CN103801392A

CN103801392A - Catalyst for removing nitrogen oxides and method for producing same

Info

Publication number: CN103801392A
Application number: CN201410067421.6A
Authority: CN
Inventors: 松尾武士; 武胁隆彦; 西冈大辅; 大岛一典; 陈海军; 垣内博行
Original assignee: Mitsubishi Plastics Inc
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2009-01-22
Filing date: 2010-01-21
Publication date: 2014-05-21
Also published as: US20120020875A1; US20160082425A1; EP2380663A1; CN102292156A; JP2015013287A; WO2010084930A1; JP6072207B2; US20120028789A1; CN102292156B; EP2380663A4; JP5876549B2; JP2016055287A; JPWO2010084930A1; US20150133287A1; JP5730584B2; US20130005563A1

Abstract

The object is to provide an exhaust gas purification catalyst that exhibit high nitrogen oxide purification performance, and to provide a simple and efficient method for producing the catalyst, in which the amount of the waste liquid is reduced, further, an object of the invention is to provide a zeolite-containing catalyst for purifying nitrogen oxides, which does not use an expensive noble metal or the like and which has high nitrogen oxide purification performance. The present invention relates to a catalyst for purifying nitrogen oxides, which comprises: zeolite at least containing an aluminium atom and a phosphorus atom in the skeleton structure thereof; and a metal supported on the zeolite, wherein a fluctuation coefficient of intensity of the metal is at least 20%, when performing an element mapping of the metal in the catalyst with an electron probe microanalyzer, and, a catalyst for purifying nitrogen oxides, which comprises the zeolite containing at least a silicon atom, a phosphorus atom and an aluminium atom, and having an adsorption retention rate of at least 80% in a water vapor repetitive adsorption/desorption test at 90 DEG C.

Description

Catalyst for cleaning up nitrogen oxides and manufacture method thereof

The application is the divisional application based on following Chinese patent application:

The original bill applying date: on January 21st, 2010

Original bill application number: 201080005585.6 (PCT/JP2010/050737)

Original bill application title: catalyst for cleaning up nitrogen oxides and manufacture method thereof

Technical field

The present invention relates to catalyst for cleaning up nitrogen oxides, relate in particular to the catalyst that contains zeolite (following, to be only referred to as zeolite catalyst) that can purify nitrogen oxide contained the waste gas of discharging from internal combustion engines such as Diesel engines and the method for effectively manufacturing zeolite catalyst.

Background technology

The contained nitrogen oxide such as waste gas or plant gas that internal combustion engine is discharged is to use V ₂o ₅-TiO ₂catalyst and ammonia, by SCR (SCR:Selerctive Catalytic Reduction), purify., V ₂o ₅-TiO ₂catalyst is due at high temperature distillation, and catalyst component is likely discharged from waste gas, so be not suitable for especially the waste gas purification of the moving bodys such as automobile.

Therefore, in recent years, proposed a kind of in automobile, special in the more difficult diesel locomotive of the purification of nitrogen oxide, as the zeolite catalyst that is carried with metal of SCR catalyst.

Especially, in the known zeolite having CHA structure, hold metal, for the purification of nitrogen oxide, it can become highly active catalyst.For example, patent documentation 1 proposes to hold the catalyst of catalytic metal in crystalline state material SAPO porous carrier.The document proposes the exhaust gas purification catalyst obtaining by the following method, by ammonium ion (NH ₄ ⁺) crystallographic SAPO (following, be sometimes referred to as SAPO) is carried out after ion-exchange, then hold catalytic metal with ion-exchange process.

In addition, patent documentation 2 proposes to be carried with the catalyst of copper on the zeolite with 8 ring structures.

On the other hand, demonstrate highly active exhaust gas purification catalyst as the purification of the nitrogen oxide in oxygen excess atmosphere, have document to propose to coexist on the porous carrier of SAPO to be carried with the catalyst (patent documentation 3) of easy oxidation metal and platinum group metal.

On the other hand, as the method that holds metal on zeolite, except the ion-exchange that above-mentioned patent documentation 1 is recorded, can also make with the following method, according to the moisture content of carrier, make to carry out heat drying after carrier absorption source metal solution, or the moisture filter cake that filter pulp obtains is excessively dried.

, we think, these methods are for except anhydrating or solvent, need to be at high temperature dried for a long time, so acid or alkali when dry in water cause zeolite structured avalanche, or the metal dispersion on zeolite is poor, can not get being equal to or being better than the performance while adopting ion-exchange.

On the other hand, in patent documentation 4, hold method as other of catalyst, pointed out spray drying process.

Prior art document

Patent documentation

Patent documentation 1: Japanese patent laid-open 7-155614 communique

Patent documentation 2: No. 2008/118434th, International Publication

Patent documentation 3: Japanese patent laid-open 2-293049 communique

Patent documentation 4: Japanese Patent Laid-Open 2009-022842 communique

Summary of the invention

The problem that invention will solve

, there is the inadequate problem of degrading activity of NOx under 200 ℃ of following low temperature in the catalyst described in patent documentation 1.In addition, exist a large amount of waste liquid to discharge by ion-exchange manufacture, or need to filter slurry, problem that cleaning etc. is manufactured.

In addition,, though the catalyst described in patent documentation 2 can reduce and remove NOx under oxidizing atmosphere, inventor, by research, has understood fully heat resistance and the durability insufficient of these zeolites.

In addition, the platinum group metal that the exhaust gas purification catalyst that patent documentation 3 proposes comprises high price, and the purifying rate of nitrogen oxide insufficient, be 50% left and right, therefore practical existing problems.

The nitrous oxides exhaust gas catalyst for clarifying that provides a kind of purifying property high is provided problem of the present invention, and a kind of easy and efficient in the manufacture of described catalyst, manufacture method that waste liquid amount is few is provided.

Further, problem of the present invention is to provide a kind of catalyst that contains zeolite that can purifying nitrogen oxide, and it does not use the precious metal of high price, and active high.

Solve the means of problem

The inventor is through scrutinizing, found that, on zeolite, hold in the catalyst for cleaning up nitrogen oxides of metal, under specific state, on zeolite, hold the catalyst of metal, compared with adopting the catalyst for cleaning up nitrogen oxides of the method that holds in the past, its NOx gas cleaning performance improves, and the purifying property under low temperature is also good in addition, thereby has completed the present invention.

The inventor is through scrutinizing, and result also finds to have the specific steam SAPO of characterization of adsorption (following, SAPO) repeatedly, the purifying property of nitrogen oxide is high, it is shocking, under low temperature, purifying property is high, and durability is also good, the suitable SCR catalyst that is used as.Particularly, find as SCR catalyst, preferably for the thing of the durability height of the adsorption desorption of steam, preferably there is the thing of specific water vapor adsorption characteristic, the SAPO that preferably adopts specific manufacture method, also preferably has the thing of specific physical property, thereby has completed the present invention.

The inventor by removing after decentralized medium within the utmost point short time from the mixture that contains zeolite and source metal, under gas communication, fire, result is found amazedly, can obtain following catalyst, it is compared with adopting the catalyst for cleaning up nitrogen oxides of the method that holds in the past, NOx gas cleaning performance is improved, and purifying property under low temperature is also good, thereby has completed the present invention.

Namely, main points of the present invention are as follows.

[1] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, in skeleton structure, at least to contain the catalyst for cleaning up nitrogen oxides that is carried with metal on the zeolite of aluminium atom and phosphorus atoms, while using transmission electron microscope observation, the metal holding in catalyst is held (the 1st mode of catalyst of the present invention) as the particle of diameter 0.5nm to 20nm.

[2] according to the catalyst for cleaning up nitrogen oxides [1] described, it is characterized in that, under the atmosphere that contains 10% steam, at 800 ℃, described catalyst was carried out to steam treatment after 5 hours, while using transmission electron microscope observation, the metal holding in catalyst is to be that 0.5nm particle above, below 20nm is held as diameter.

[3] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, in skeleton structure, at least to contain the catalyst for cleaning up nitrogen oxides that is carried with metal on the zeolite of aluminium atom and phosphorus atoms, while carrying out the element drawing of the metal in catalyst with electron probe microanalyzer, the coefficient of variation of the intensity of metal is more than 20% (the 2nd mode of catalyst of the present invention).

[4] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, in skeleton structure, to there is the catalyst for cleaning up nitrogen oxides that is carried with metal on the zeolite of 8 ring structures, carry out element when drawing of the metal in catalyst with electron probe microanalyzer, the coefficient of variation of the intensity of metal is more than 20% (catalyst of the present invention the 3rd mode).

[5] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, in skeleton structure, at least to contain the catalyst for cleaning up nitrogen oxides that is carried with metal on the zeolite of aluminium atom and phosphorus atoms, in ammonia TPD (thermal desorption) method, the peak temperature of the ammonia desorb after the steam treatment of catalyst is (the 4th mode of catalyst of the present invention) between 250 ℃ to 500 ℃.

[6] according to the catalyst for cleaning up nitrogen oxides [5] described, it is characterized in that, the ammonia adsorbance in ammonia TPD (pyrolysis is analysed) method of described catalyst is more than 0.6mol/kg.

[7] according to the catalyst for cleaning up nitrogen oxides described in any one of [1]～[6], described zeolite also contains silicon atom.

[8] according to the catalyst for cleaning up nitrogen oxides described in any one of [1]～[7], under the atmosphere that contains 10% steam, at 800 ℃, described zeolite was carried out to steam treatment after 10 hours, measure solid ²⁹when Si-DD/MAS-NMR wave spectrum, with respect to the integrated intensity area of-75～-125ppm signal strength signal intensity, the integrated intensity area of-105～-125ppm signal strength signal intensity is below 25%.

[9] according to the catalyst for cleaning up nitrogen oxides described in any one of [1]～[8], the structure of described zeolite is CHA in the code of IZA regulation.

[10] according to the catalyst for cleaning up nitrogen oxides [8] or [9] described, the silicon atom contained skeleton structure of described zeolite is made as to x with respect to the ratio that exists of the total of silicon atom, aluminium atom, phosphorus atoms, the ratio that exists of aluminium atom is made as y, phosphorus atoms exist ratio to be made as z time, x is more than 0, below 0.3, and y is more than 0.2, below 0.6, and z is more than 0.3, below 0.6.

[11] according to the catalyst for cleaning up nitrogen oxides described in any one of [1]～[10], described metal is Cu or Fe.

[12] according to the catalyst for cleaning up nitrogen oxides described in any one of [1]～[11], it is characterized in that, by the described zeolite of modulation and the source metal of described metal and the mixture of decentralized medium, be dried and remove decentralized medium by spraying, manufacture.

[13] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, it is the catalyst for cleaning up nitrogen oxides that contains zeolite, this catalyst at least contains silicon atom, phosphorus atoms, aluminium atom, the steam of measuring at 90 ℃ is repeatedly in adsorption desorption test, and Adsorption Dimension holdup is more than 80% (catalyst of the present invention the 5th mode).

[14] according to the catalyst for cleaning up nitrogen oxides [13] described, in the described steam front and back of adsorption desorption test repeatedly, when water adsorption amount while measuring the relative vapour pressure 0.2 of measuring in 25 ℃ of water vapor adsorption isotherms of this catalyst, the ratio of the water adsorption amount of the water adsorption amount after described test before with respect to described test is more than 0.7.

[15] catalyst for cleaning up nitrogen oxides according to [13] or [14], is characterized in that, zeolite at least contains silicon atom, phosphorus atoms, aluminium atom, and the steam of measuring in the time of 90 ℃ is repeatedly in adsorption desorption test, and Adsorption Dimension holdup is more than 80%.

[16] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, it is the catalyst for cleaning up nitrogen oxides that contains zeolite, this zeolite at least contains silicon atom, phosphorus atoms, aluminium atom, the steam of measuring in the time of 90 ℃ is repeatedly in adsorption desorption test, and Adsorption Dimension holdup is more than 80% (the 6th mode of catalyst of the present invention).

[17] according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[16], in the described steam front and back of adsorption desorption test repeatedly, when water adsorption amount while measuring the relative vapour pressure 0.2 of measuring in 25 ℃ of water vapor adsorption isotherms of described zeolite, the ratio of the water adsorption amount of the water adsorption amount after described test before with respect to described test is more than 0.7.

[18] according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[17], under the atmosphere that contains 10% steam, at 800 ℃, described zeolite was carried out to steam treatment after 10 hours, measure solid ²⁹when Si-DD/MAS-NMR wave spectrum, the integrated intensity area of-105～-125ppm signal strength signal intensity is below 25% with respect to the integrated intensity area of-75～-125ppm signal strength signal intensity.

[19] according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[18], about described catalyst, use in the X-ray diffraction mensuration of CuK α at x-ray source, except the peak from zeolite, also in being the scope more than 21.2 degree, below 21.6 degree, the angle of diffraction (2 θ) observes diffraction maximum.

[20] according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[19], after described catalyst being heat-treated more than 700 ℃, while carrying out described X-ray diffraction mensuration, except the peak from zeolite, also in being the scope more than 21.2 degree, below 21.6 degree, the angle of diffraction (2 θ) observes diffraction maximum.

[21] according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[20], it is characterized in that, this zeolite is carried with metal.

[22] catalyst for cleaning up nitrogen oxides, is characterized in that, is the catalyst for cleaning up nitrogen oxides that contains zeolite, under the atmosphere that contains 10% steam, at 800 ℃, described zeolite is carried out to steam treatment after 10 hours, measures solid ²⁹when Si-DD/MAS-NMR wave spectrum, the integrated intensity area of-105～-125ppm signal strength signal intensity is (the 7th mode of catalyst of the present invention) below 25% with respect to the integrated intensity area of-75～-125ppm signal strength signal intensity.

[23] according to the catalyst for cleaning up nitrogen oxides [22] described, the average grain diameter of zeolite is more than 1 μ m, and the skeleton structure of described zeolite at least contains silicon atom, phosphorus atoms, aluminium atom.

[24] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, on zeolite, be carried with metal and form, the skeleton structure of described zeolite at least contains silicon atom, phosphorus atoms, aluminium atom, and the average grain diameter of described zeolite is 1 μ m above (the 8th mode of catalyst of the present invention).

[25] catalyst for cleaning up nitrogen oxides according to [23] or [24], in the skeleton structure by silicon atom with respect to zeolite the total of contained aluminium atom, silicon atom, phosphorus atoms exist ratio to be made as x time, x is more than 0.05, below 0.11,

[26] according to the catalyst for cleaning up nitrogen oxides described in any one of [22]～[25], described catalyst uses in the X-ray diffraction mensuration of CuK α at x-ray source, except the peak from zeolite, in the angle of diffraction (2 θ) be more than 21.2 degree also, scope below 21.6 degree observes diffraction maximum.

[27] according to the catalyst for cleaning up nitrogen oxides described in any one of [22]～[26], after described catalyst being heat-treated more than 700 ℃, while carrying out described X-ray diffraction mensuration, except the peak from zeolite, also in being the scope more than 21.2 degree, below 21.6 degree, the angle of diffraction (2 θ) observes diffraction maximum.

[28] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, on zeolite, being carried with metal forms, described catalyst uses in the X-ray diffraction mensuration of CuK α at x-ray source, except the peak from zeolite, also in being the scope more than 21.2 degree, below 21.6 degree, the angle of diffraction (20) observes diffraction maximum (the 9th mode of catalyst of the present invention).

[29] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, in skeleton structure, at least contain on the zeolite of aluminium atom and phosphorus atoms and be carried with metal, in infrared ray absorbing (IR) spectral differences of the front and back of the described catalyst absorption nitric oxide (NO) of measuring, between 1860～1930cm-1, there is plural absorbing wavelength (the 10th mode of catalyst of the present invention) at 25 ℃.

[30] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, in skeleton structure, at least contain on the zeolite of aluminium atom and phosphorus atoms and be carried with metal, in infrared ray absorbing (IR) spectral differences of the front and back of the described catalyst absorption nitric oxide (NO) of measuring at 150 ℃, 1525～1757cm ^-1the maximum of peak intensity with respect to 1757～1990cm ^-1the ratio of maximum of peak intensity be (the 11st mode of catalyst of the present invention) below 1.

[31] a kind of catalyst for cleaning up nitrogen oxides, it is characterized in that, in skeleton structure, at least contain on the zeolite of aluminium atom and phosphorus atoms and be carried with copper, have the peak (the 12nd mode of catalyst of the present invention) of the electron spin resonance (ESR) of the two or more copper from described catalyst (II) ion.

[32] catalyst for cleaning up nitrogen oxides according to [31], is characterized in that, from the g value at the peak of the electron spin resonance (ESR) of copper (II) ion of described catalyst between 2.3 to 2.5.

[33] according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[32], the ratio that exists of the silicon atom of the total of the silicon atom contained skeleton structure with respect to described zeolite, aluminium atom, phosphorus atoms is made as to x, the ratio that exists of aluminium atom is made as y, phosphorus atoms exist ratio to be made as z time, x is more than 0.05, below 0.11, and y is more than 0.3, below 0.6, and z is more than 0.3, below 0.6.

[34] according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[33], after silicon atom raw material, aluminium atomic raw material, phosphorus atoms raw material and template are mixed, carry out Hydrothermal Synthesis, while manufacturing zeolite, as template, use from (1) and contain the template of nitrogen as the more than a kind compound of selecting in each group heteroatomic ester ring type heterocyclic compound, these two groups of (2) alkylamine.

[35], according to the catalyst for cleaning up nitrogen oxides described in any one of [13]～[34], it is zeolite structured that this zeolite stipulates in IZA is CHA.

[36] a kind of manufacture method of catalyst for cleaning up nitrogen oxides, it is characterized in that, the zeolite that at least contains aluminium atom and phosphorus atoms in skeleton structure is carried with metal, modulate the source metal of described zeolite, described metal and the mixture of decentralized medium, remove after the decentralized medium in described mixture, fire, and carried out removing of described decentralized medium with 60 minutes following time.

[37] according to the manufacture method of the catalyst for cleaning up nitrogen oxides [36] described, the skeleton structure of zeolite has 8 ring structures.

[38] a kind of manufacture method of catalyst for cleaning up nitrogen oxides, it is characterized in that, the zeolite that skeleton structure has 8 ring structures is carried with metal, modulate the source metal of described zeolite, described metal and the mixture of decentralized medium, remove after the decentralized medium in described mixture, fire, and carried out removing of described decentralized medium with 60 minutes following time.

[39] according to the manufacture method of the catalyst for cleaning up nitrogen oxides described in any one of [36]～[38], it is characterized in that, described mixture contains template.

[40] according to the manufacture method of the catalyst for cleaning up nitrogen oxides described in any one of [36]～[39], it is characterized in that, by the dry decentralized medium of removing of spraying.

[41] according to the manufacture method of the catalyst for cleaning up nitrogen oxides described in any one of [36]～[40], described zeolite also contains silicon atom.

[42] according to the manufacture method of the catalyst for cleaning up nitrogen oxides described in any one of [36]～[41], the structure of described zeolite is CHA in the code of IZA regulation.

[43] according to the manufacture method of the catalyst for cleaning up nitrogen oxides described in any one of [36]～[42], described metal is Cu or Fe.

[44], according to the manufacture method of the catalyst for cleaning up nitrogen oxides described in any one of [36]～[43], in spraying is dry, the temperature that makes it the thermal medium of contact for described mixture is dried is 80 ℃～350 ℃.

[45] mixture, the catalyst for cleaning up nitrogen oxides described in any one that contains at least one and [13]～[35] in the compound shown in formula (I) and silicic acid liquid.

[changing 1]

(wherein, in formula (I), R is independently of one another can substituted alkyl, aryl, alkenyl, alkynyl, alkoxyl or phenoxy group, R ' separately independent be can substituted alkyl, aryl, alkenyl or alkynyl, n is 1 to 100 number.〕

[46] according to the mixture [45] described, contain inorfil.

[47] according to the mixture [45] or [46] described, with respect to catalyst for cleaning up nitrogen oxides 100 weight portions, the compound shown in formula (I) is converted into oxide, contains 2～40 weight portions.

[48] formed body, is obtained by the mixture described in any one of [45]～[47].

[49] according to the formed body [48] described, it is shaped as cellular.

[50] a purification of nitrogen oxides element, is characterized in that, the catalyst for cleaning up nitrogen oxides described in any one of [1]～[35] is coated on cellular formed body and obtains.

[51] a purification of nitrogen oxides element, is characterized in that, is shaped and is obtained by the catalyst for cleaning up nitrogen oxides described in any one of [1]～[35].

[52] a purification of nitrogen oxides system, is characterized in that, uses [50] or [51] described catalyst for cleaning up nitrogen oxides element.

The effect of invention

According to the present invention, can obtain the high catalyst of purifying property under the detergence(-cy) high and low temperature of nitrogen oxide, can also easy and effectively manufacture the catalyst that purifying property is high.In addition, can obtain such catalyst, when reality is used this catalyst, even under the condition of repeatedly carrying out at the adsorption and desorption of water, also there is long-term persistence.

Accompanying drawing explanation

[Fig. 1] is the TEM image of the catalyst 2 described in embodiment 2A.

[Fig. 2] is catalyst 2 described in the embodiment 2A TEM image after steam treatment.

[Fig. 3] is the Si of EMPA and the element spectrogram of Cu of the catalyst 2 described in embodiment 2A.

[Fig. 4] is the NO-IR spectrum that the catalyst 2 described in embodiment 2A is at room temperature measured.

[Fig. 5] is the NO-IR spectrum that the catalyst 2 described in embodiment 2A is measured at 150 ℃.

[Fig. 6] is the ESR spectrum of the catalyst 2 described in embodiment 2A.

[Fig. 7] is the TEM image of the catalyst 8 described in comparative example 5A.

[Fig. 8] is catalyst 8 described in the comparative example 5A TEM image after steam treatment.

[Fig. 9] is the Si of EMPA and the element spectrogram of Cu of the catalyst 8 described in comparative example 5A.

[Figure 10] is the NO-IR spectrum that the catalyst 8 described in comparative example 5A is at room temperature measured.

[Figure 11] is the NO-IR spectrum that the catalyst 8 described in comparative example 5A is measured at 150 ℃.

[Figure 12] is the ESR spectrum of the catalyst 8 described in comparative example 5A.

[Figure 13] is the zeolite described in embodiment 1B ²⁹the measurement result of Si-NMR.

[Figure 14] is the zeolite described in comparative example 3B ²⁹the measurement result of Si-NMR.

[Figure 15] is the X-ray diffraction measurement result of the catalyst described in embodiment 2B.

[Figure 16] is catalyst described in the embodiment 2B X-ray diffraction measurement result after 800 ℃ of heat treatment.

[Figure 17] is the X-ray diffraction measurement result of the catalyst described in embodiment 3B.

[Figure 18] is catalyst described in the embodiment 3B X-ray diffraction measurement result after 800 ℃ of heat treatment.

[Figure 19] is the X-ray diffraction measurement result of the catalyst described in comparative example 3B.

[Figure 20] is catalyst described in the comparative example 3B X-ray diffraction measurement result after 800 ℃ of heat treatment.

[Figure 21] is the SEM photo of the zeolite described in embodiment 1B.

[Figure 22] is the SEM photo of the zeolite described in comparative example 3B.

The specific embodiment

Below, be described in detail with regard to embodiments of the present invention, but following explanation is an example (typical example) of embodiments of the present invention, is not to specify these contents.In addition, " quality % ", " quality ppm " and " mass parts " respectively with " % by weight ", " ppm by weight " and " weight portion " synonym.

" the 5th mode～12nd mode of the 1st mode～4th mode of catalyst and catalyst "

Below, the 1st mode～12nd mode of catalyst of the present invention is described in detail.

< nitrogen oxide and purification > thereof

The nitrogen oxide purifying by object catalyst of the present invention has nitric oxide, nitrogen dioxide, nitrous oxide etc. for example.In addition, below, sometimes their unifications are called to NOx class.In this description, purifying nitrogen oxide is to instigate nitrogen oxide to react on catalyst, changes into nitrogen and oxygen etc.

Now, nitrogen oxide can directly react, and also can, for the object that improves purification efficiency, coexist in catalyst with reducing agent.Reducing agent can use ammonia, urea, organic amine, carbon monoxide, hydrocarbon, hydrogen etc., preferably uses ammonia, urea.

< catalyst >

Object catalyst of the present invention is described above, refer to can purifying nitrogen oxide catalyst, specifically refer to the catalyst for cleaning up nitrogen oxides that contains zeolite.(following, be sometimes only referred to as catalyst.)

< zeolite >

Zeolite in the present invention refers to the zeolites of International Zeolite Association (International Zeolite Association) (following IZA) regulation, particularly, as zeolite, have for example at least and (below, be sometimes referred to as aluminum phosphate class containing aerobic, aluminium (Al), phosphorus (P) as the material of the atom that forms skeleton structure.), at least (below, be sometimes referred to as aluminosilicate-type containing aerobic, aluminium, silicon (Si) as the material of the atom that forms skeleton structure.)。

Aluminum phosphate class refers to a class that at least forms the atom of skeleton structure containing aerobic, aluminium (Al), phosphorus (P) conduct, and a part for these atoms can be replaced by other atom (Me).Other atoms (Me) have the atom of at least a kind of element in 3B family and the 4B family element beyond the 2A family that is for example selected from the periodic table of elements, 3A family, 4A family, 5A family, 7A family, 8 families, 1B family, 2B family, aluminium for example.Wherein, Me mono-aluminum phosphate that preferably phosphorus atoms is replaced by hetero atom (Mel: wherein, Mel is the 4B family element of the periodic table of elements).

Mel can contain one, also can contain two or more.Preferably, Mel is silicon or germanium, further preferred silicon.Namely, the aluminum phosphate more preferably being replaced by silicon is SAPO.

Mel, the Al of skeleton structure and the composition (mol ratio) of P that form aluminum phosphate class are not particularly limited, Mel is made as to x1 with respect to the mol ratio of the total of Mel, Al, P, the mol ratio of Al is made as y1, when the mol ratio of P is made as z1, x1 is generally more than 0, preferably more than 0.01, common below 0.3.

In addition, described y1 is generally more than 0.2, preferably more than 0.3, common below 0.6, preferably below 0.5.

In addition, described z1 is generally more than 0.3, preferably more than 0.4, is generally below 0.6, preferably below 0.5.

In the present invention the zeolite that uses during for SAPO, the ratio that exists of aluminium atom, phosphorus atoms and the silicon atom in zeolite is preferably following formula (I), (II) and (I II).

0.05≤x1≤0.11…(I)

(in formula, x1 represents the mol ratio of silicon with respect to the total of silicon, aluminium and the phosphorus of skeleton structure)

0.3≤y1≤0.6…(II)

(in formula, y1 represents the mol ratio of aluminium with respect to the total of silicon, aluminium and the phosphorus of skeleton structure)

0.3≤z1≤0.6…(III)

(in formula, z1 represents the mol ratio of phosphorus with respect to the total of silicon, aluminium and the phosphorus of skeleton structure)

In other words the meaning is to be preferably as follows zeolite, with respect to the total of silicon atom contained in the skeleton structure in zeolite, aluminium atom, phosphorus atoms, the ratio that exists of silicon atom is made as to x1, the ratio that exists of aluminium atom is made as y1, phosphorus atoms exist ratio to be made as z1 time, x1 is generally more than 0.05, below 0.11, and y1 is generally more than 0.3, below 0.6, and z1 is generally more than 0.3, below 0.6.

Further be preferably as follows zeolite, x1 is preferably more than 0.06, more preferably more than 0.07, further preferably more than 0.075, is generally below 0.11, preferably below 0.105, more preferably below 0.100, further preferably below 0.095.

In addition, in the zeolitic frameworks of the zeolite in the present invention, can contain other elements.Other elements there can be exemplified lithium, magnesium, titanium, zirconium, vanadium, chromium, manganese, iron, cobalt, nickel, palladium, copper, zinc, gallium, germanium, arsenic, tin, calcium, boron etc.Preferable examples has iron, copper, gallium.

The content of other elements is with respect to the mol ratio of the total of the silicon in zeolitic frameworks, aluminium and phosphorus preferably below 0.3, further preferably below 0.1.

In addition, the ratio of above-mentioned element determines by elementary analysis, and the elementary analysis in the present invention is carried out as follows, and heating is dissolved in aqueous hydrochloric acid solution sample, obtain by inductively coupled plasma (Inductively Coupled Plasma, below ICP) emission spectrographic analysis.

Aluminosilicate-type refers to a class that at least forms the atom of skeleton structure containing aerobic, aluminium (Al), silicon (Si) conduct, and a part for these atoms can be replaced by other atoms (Me2).

Form Me2, the Al of skeleton structure and the composition (mol ratio) of Si of aluminosilicate-type and be not particularly limited, but with respect to the total of Me2, Al, Si, the mol ratio of Me2 is made as to x2, the mol ratio of Al is made as y2, when the mol ratio of Si is made as z2, x2 is generally more than 0, below 0.3.When x2 is greater than higher limit, there is the tendency of easily sneaking into impurity while synthesizing.

In addition, described y2 is generally more than 0.001, preferably more than 0.02, is generally below 0.5, preferably below 0.25.

In addition, described z2 is generally more than 0.5, preferably more than 0.75, is generally below 0.999, preferably below 0.98.

Y2, z2 outside above-mentioned scope time, have synthetic difficulty, or acid position are very few, and are not shown the situation of NOx degrading activity.

Other atoms Me2 can contain a kind of or two or more.Preferably Me2 is the element that belongs to the periodic table of elements the 3rd or the 4th cycle.

The zeolite that catalyst of the present invention preferably uses is the zeolite that skeleton structure at least contains oxygen atom, aluminium atom and phosphorus atoms, more preferably crystallographic aluminum phosphate class.Preferred crystal SAPO further.

The skeleton structure > of < zeolite

Zeolite is generally crystallographic, has the SiO of methane type ₄tetrahedron, AlO ₄tetrahedron or PO ₄tetrahedron (following, they are summarized and are called TO ₄, the atom outside the oxygen containing is referred to as to T atom) the oxygen atom on each summit connect by sharing the regular mesh-like structure that forms.T atom is also known as the atom outside Al, P, Si.One of elementary cell of mesh structure is 8 TO ₄the ring-type that tetrahedron is formed by connecting, calls it as 8 rings.Equally, 6 rings, 10 rings etc. are also zeolite structured elementary cells.

In addition, the structure of the zeolite in the present invention is determined by X-ray diffraction method (X-ray diffraction, following XRD).

The zeolite preferably using in the present invention is the zeolite in skeleton structure with 8 ring structures.

The following zeolite of coding that the concrete zeolite with 8 ring structures has International Zeolite Association (International Zeolite Association) (IZA) to stipulate for example, i.e. ABW, AEI, AEN, AFN, AFR, AFS, AFT, AFX, AFY, ANA, APC, APD, ATN, ATT, ATV, AWO, AWW, BCT, BIK, BPH, BRE, CAS, CDO, CGF, CGS, CHA, CLO, DAC, DDR, DFO, DFT, EAB, EDI, EON, EPI, ERI, ESV, ETR, FER, GIS, GME, GOO, HEU, IHW, ITE, ITW, IWW, JBW, KFI, LAW, LEV, LOV, LTA, MAZ, MER, MFS, MON, MOR, MOZ, MTF, NAT, NSI, OBW, OFF, OSO, OWE, PAU, PHI, RHO, RRO, RSN, RTE, RTH, RWR, SAS, SAT, SAV, SBE, SFO, SIV, SOS, STI, SZR, THO, TSC, UEI, UFI, VNI, VSV, WEI, WEN, YUG, ZON, wherein, from the viewpoint of catalyst activity, is preferably selected from CHA, FER, GIS, LTA, any one of MOR, particularly preferably CHA.

The zeolite preferably using in the present invention has aluminum phosphate, alumina silicate for example, use particularly the words of the coded representation of International Zeolite Association (IZA) regulation, preferably there is aluminum phosphate, the alumina silicate of any one structure of AEI, AFR, AFS, AFT, AFX, AFY, AHT, CHA, DFO, ERI, FAU, GIS, LEV, LTA, VFI, more preferably any one of AEI, AFX, GIS, CHA, VFI, AFS, LTA, FAU, AFY, consider preferably there is the zeolite of CHA structure from being difficult for absorption from the hydrocarbon this respect of fuel.

Zeolites in the present invention more preferably skeleton structure at least contains the aluminum phosphate class of aluminium atom and phosphorus atoms, and has the zeolite of 8 ring structures.

Zeolites in the present invention, except the constituent of the skeleton structure that has as elementary cell, can also contain and have the composition that can carry out with other cations the cationic of ion-exchange.Cation is now not particularly limited, and has for example the alkali elements such as proton, Li, Na, K, the alkali earths elements such as Mg, Ca, and the rare earth elements such as La, Ce etc., wherein, preferably proton, alkali element, alkali earths element.

The skeletal density (below sometimes referred to as FD) of the zeolites in the present invention is not particularly limited, and is generally 13.0T/nm ³above, preferred 13.5T/nm ³above, more preferably 14.0T/nm ³above, be generally 20.0T/nm ³below, preferred 19.0T/nm ³below, more preferably 17.5T/nm ³below.In addition, skeletal density (T/nm ³) refer to the per unit volume nm of zeolite ³the quantity of the T atom (atom of the element beyond the oxygen of the skeleton of formation zeolite) existing, this value is by the structures shape of zeolite.When less than described lower limit, there is structural unstable situation, or the tendency that has persistence to reduce, on the other hand, while exceeding described higher limit, the situation that exists adsorbance, catalyst activity to diminish, or be not suitable for the situation as catalyst.

Zeolite in the present invention preferably has the zeolite of following water vapor adsorption characteristic, and, in the scope of certain specific vapour pressure relatively, larger variation occurs the adsorbance of water.The words that adopt adsorption isotherm to evaluate, be generally following zeolite, in the water vapor adsorption isotherms of 25 ℃, in scope in relative vapour pressure more than 0.03, below 0.25, when there is 0.05 variation in vapour pressure relatively, more than the adsorbance of water is changed to 0.10g/g, preferably more than 0.15g/g.

Relatively the preferable range of vapour pressure is more than 0.035, below 0.15, further preferably more than 0.04, below 0.09.In addition,, although the adsorbance of preferred water changes greatly, adsorbance is poor larger, is generally below 1.0g/g.

Zeolite in the present invention, the steam of measuring at as described below 90 ℃ is repeatedly in adsorption desorption test, the preferably high person of Adsorption Dimension holdup, conventionally Adsorption Dimension holdup is more than 80%, preferably more than 90%, more preferably more than 95%, the upper limit is not particularly limited, and is generally below 100%.

Zeolite in the present invention is preferred, repeats in adsorption desorption test at steam described later, and Adsorption Dimension holdup is more than 80%.Zeolite in the present invention, its carry out at 90 ℃ the steam measured repeatedly the water adsorption amount after adsorption desorption test be the water adsorption amount of 0.2 o'clock with respect to relative vapour pressure, preferably more than 70%, more preferably more than 80%, further preferably more than 90%.The upper limit is not particularly limited, and is generally below 100%, preferably below 95%.

Steam repeatedly adsorption desorption test is repeatedly to proceed as follows, and sample is remained in the vacuum tank that maintains T ℃, respectively at T ₁℃ saturated steam atmosphere under and T ₂under ℃ saturated steam atmosphere, expose 90 seconds kind (T ₁<T ₂<T).Now, at T ₁℃ saturated steam atmosphere under, sample is exposed to T ₂℃ saturated steam atmosphere time the water that adsorbs part generation desorption, to maintaining T ₁℃ tank move.By from be adsorbed onto for the m time the n time desorption to T ₁℃ the tank total amount (Qn:m (g)) of water and the dry weight (W (g)) of sample that move, obtain each average adsorbance (Cn:m (g/g)) by following formula.

[Cn：m]＝[Qn：m]／(n-m+1)／W

Conventionally, absorption, desorption carry out more than 1000 times repeatedly, and preferably more than 2000 times, the upper limit is not particularly limited and (above operation is called to " T-T ₂-T ₁steam adsorption desorption test repeatedly ").

The steam of the zeolite using in the present invention repeatedly adsorption desorption test proceeds as follows repeatedly, remain on by zeolite sample in the vacuum tank that maintains 90 ℃, in the saturated steam atmosphere of 5 ℃ He in 80 ℃ of saturated steam atmosphere, exposed for 90 seconds respectively.Obtain each average adsorbance (Cn:m (g/g)) (the adsorption desorption test repeatedly of the steam of 90-80-5 is called above operation " steam of measuring at 90 ℃ adsorption desorption test repeatedly " sometimes) according to the above-mentioned numerical value obtaining thus.

The sustainment rate of desorption test refers to the value of the ratio of the average adsorbance of the described steam average adsorbance of the 1001st time to the 2000th time that adsorption desorption is tested repeatedly of trying to achieve with respect to the 1st time to the 1000th time.Even the high adsorption desorption that represents repeatedly to carry out water of the sustainment rate of average adsorbance, zeolite can be not deteriorated yet.Sustainment rate is preferably more than 80%, more preferably more than 90%, further preferably more than 95%.On be limited to and can not occur deteriorated 100% completely.

The variation of the steam zeolite that adsorption desorption causes repeatedly can be observed by the variation of the water vapor adsorption isotherms of the zeolite before and after test.

By repeatedly carrying out the adsorption desorption of water, the structure of zeolite does not have vicissitudinous words, and water vapor adsorption isotherms just can not change, and in the time of the variations such as the structure of zeolite is damaged, can observe adsorbance and reduce.At 90 ℃, carry out the adsorption desorption test repeatedly of 2000 steam, before test, vapour pressure is that the water adsorption amount of 0.2 o'clock is generally more than 70% relatively at 25 ℃ after test, preferably more than 80%, further preferably more than 90%.

Zeolite of the present invention is because the steam Adsorption Dimension holdup that adsorption desorption is tested is repeatedly high, so the purification excellence of nitrogen oxide.Catalyst loading of the present invention is in enterprising enforcement used times such as automobiles, we think and are actually the adsorption desorption that repeatedly carries out water, carry out the purification of nitrogen oxide, therefore we think while repeatedly carrying out the repetition adsorption desorption of water not and can deteriorated catalyst to have the structure of waste gas purification ability excellence, have the detergent power of excellent in practical nitrogen oxide.

The particle diameter of the zeolite in the present invention refers in the time of observed under electron microscope zeolite, and the mean value of the primary particle size of the zeolite particles of any 10～30, more than being generally 1 μ m, further preferably more than 2 μ m, more preferably more than 3 μ m, be generally below 15 μ m, preferably below 10 μ m.In addition, the particle diameter of the zeolite in the present invention refers in the manufacture of the zeolite of following explanation, the value of measuring as the particle diameter of removing after template.

At the atmosphere that contains 10% steam, 800 ℃, the zeolite in the present invention is carried out, after the steam treatment of 10 hours, carry out vacuum drying, it is measured to solid ²⁹when Si-DD/MAS-NMR wave spectrum, conventionally preferably near-110ppm, the little person of integrated intensity area of signal strength signal intensity.

Silicon atom in zeolitic frameworks is taked Si (OX) n (OY) 4-n conventionally, and (X, Y represent the atoms such as Al, P, Si; N=0～2) bond of type closes.Solid ²⁹near the peak observing-95ppm in Si-DD/MAS-NMR is equivalent to the situation that X, Y are the atoms beyond silicon atom.And near the peak-110ppm is equivalent to the situation that X, Y are silicon atoms, this expression has formed Si02 region.We think that using SAPO the Si position existing in skeleton is as catalyst activity point performance function when catalyst uses.Therefore, we think that silicon atom is assembled each other and form Si02 region, will become the reason that reduces of catalyst activity.Therefore, near the integrated intensity area of the signal strength signal intensity preferably-110ppm is little, particularly, the integrated intensity area of the signal strength signal intensity of-105～-125ppm is with respect to the integrated intensity area of the signal strength signal intensity of-75～-125ppm preferably below 25%, more preferably below 10%.

Zeolite in the present invention is conventionally preferred, under the atmosphere that contains 10% steam, it is carried out, after the steam treatment of 10 hours, carrying out vacuum drying at 800 ℃, measures solid ²⁹si-DD/MAS-NMR wave spectrum, in this spectrum, near the little person of integrated intensity area of the signal strength signal intensity-100ppm.

Near the peak observing-100ppm is equivalent to the situation of Si (OX) n (OY) 3-n (OH).This Si-OH base is the product of Si-O-X key or the hydrolysis of Si-O-Y key, and this part that represents the structure of zeolitic frameworks has been destroyed by steam.Zeolitic frameworks destructurized, reduces through catalyst surface area, and catalyst activity point reduces etc., causes catalyst activity reduction, and the integrated intensity area that therefore it is desirable near the signal strength signal intensity-100ppm is little.Particularly, the integrated intensity area of the signal strength signal intensity of-99～-125ppm is preferably below 40% with respect to the integrated intensity area of the signal strength signal intensity of-75～-125ppm, more preferably below 15%.

The manufacture method > of < zeolite

Zeolite in the present invention itself is known compound, can manufacture according to common institute using method.The manufacture method of the zeolite in the present invention, without special restriction, can for example be manufactured according to method Japan Patent JP 4-37007 communique, Japan Patent JP 5-21844 communique, Japan Patent JP 5-51533 communique, No. 4440871 communique of United States Patent (USP), Japanese Patent Laid-Open 2003-183020 communique, No. 4544538 communique of United States Patent (USP) etc. Suo Shu.

About the zeolite using in the present invention, conventionally, using after the atomic raw material comprising as constituting atom and the mixing of template as required, carry out Hydrothermal Synthesis, remove template, and obtain zeolite.

For aluminosilicate-type, conventionally, after aluminium atomic raw material, silicon atom raw material, (while containing other atoms Me, the further atomic raw material of other atoms (Me)) and template are as required mixed, carry out Hydrothermal Synthesis, obtain after removing template.

For aluminum phosphate class, conventionally, after aluminium atomic raw material, phosphorus atoms raw material, (while containing other atoms Me, also having the atomic raw material of other atoms (Me)) and template are as required mixed, carry out Hydrothermal Synthesis, obtain after removing template.

Below, the concrete example of the manufacture method to zeolite, contains silicon and describes as the manufacture method of the aluminum phosphate class (SAPO) of Me.

Conventionally, by by aluminium atomic raw material, phosphorus atoms raw material, silicon atom raw material, and after template as required mixes, carry out Hydrothermal Synthesis, obtain the aluminum phosphate class that contains silicon.In the time being mixed with template, conventionally after Hydrothermal Synthesis, remove template.

< aluminium atomic raw material >

Aluminium atomic raw material to the zeolite in the present invention is not particularly limited, and is generally the aluminium alkoxides such as boehmite (Pseudo-boehmite), aluminium isopropoxide, three aluminium ethylates, aluminium hydroxide, alumina sol, sodium aluminate etc., preferably boehmite.

< phosphorus atoms raw material >

The phosphorus atoms raw material of zeolite used in the present invention is generally phosphoric acid, but also can use aluminum phosphate.

< silicon atom raw material >

Silicon atom raw material to the zeolite in the present invention is not particularly limited, and is generally aerosil, silicon dioxide gel, cataloid, waterglass, silester, methyl silicate etc., preferably aerosil.

< template >

Manufacture the template that zeolite of the present invention uses and can use the various templates that use in known method, preferably template shown below.

More than one compound of every group selection ester ring type heterocyclic compound, these two groups of (2) alkylamine that template used in the present invention can contain hetero atom nitrogen from (1) uses.

(1) the ester ring type heterocyclic compound that contains hetero atom nitrogen

The heterocycle of the ester ring type heterocyclic compound that contains hetero atom nitrogen is generally 5～7 rings, preferably 6 rings.The contained heteroatomic number of heterocycle is generally below 3, preferably below 2.Hetero atom outside nitrogen is any, preferably except nitrogen, also containing aerobic.Heteroatomic position is not particularly limited, and preferably hetero atom is non-conterminous each other.

In addition, the molecular weight of the ester ring type heterocyclic compound that contains hetero atom nitrogen is generally below 250, preferably below 200, preferably below 150, in addition, is generally more than 30, preferably more than 40, further preferably more than 50 further.

The ester ring type heterocyclic compound that contains hetero atom nitrogen like this has morpholine, N-methylmorpholine, piperidines, piperazine, N for example, N '-lupetazin, 1,4-diazabicylo (2,2,2) octane, N-methyl piperidine, 3-methyl piperidine, quinuclidine, pyrrolidines, 1-METHYLPYRROLIDONE, hexamethylene imine etc., preferably morpholine, hexamethylene imine, piperidines, particularly preferably morpholine.

(2) alkylamine

The alkyl of alkylamine is generally chain-like alkyl, and in 1 molecular amine, the quantity of contained alkyl is not particularly limited, preferably 3.In addition the alkyl of alkylamine of the present invention can have the substituting groups such as a part of hydroxyl.The carbon number of the alkyl of alkylamine of the present invention is preferably below 4, and the total of the carbon number of the whole alkyl in 1 molecule is more preferably below 10.In addition, molecular weight be generally below 250, preferably below 200, further preferably below 150.

Such alkylamine has di-n-propyl amine, Tri-n-Propylamine, tri-isopropyl amine, triethylamine, triethanolamine, N for example, N-diethyl ethylene diamine, N, N-dimethylethanolamine, N methyldiethanol amine, N-methylethanolamine, two-n-butylamine, neopentyl amine, two n-amylamines, isopropylamine, tert-butylamine, ethylenediamine, diisopropylethylamine, N-methyl n-butylamine etc., preferably di-n-propylamine, Tri-n-Propylamine, Tri-n-Propylamine, triethylamine, di-n-butylamine, isopropylamine, tert-butylamine, ethylenediamine, diisopropylethylamine, N-methyl n-butylamine, particularly preferably triethylamine.

(1) desirable combination of the template of～(2) is the combination that contains morpholine, triethylamine.The blending ratio of template need to be selected according to condition.

In the time mixing two kinds of templates, conventionally, the mol ratio of two kinds of templates of mixing is 1:20 to 20:1, preferably 1:10 to 10:1, further preferred 1:5 to 5:1.

In the time mixing three kinds of templates, conventionally, the third template is 1:20 to 20:1 with respect to the mol ratio of (1) of above-mentioned mixing and the total of (2) two kinds of templates, preferably 1:10 to 10:1, further preferred 1:5 to 5:1.

In addition, the mixing ratio of two or more templates is not particularly limited, can suitably select according to condition, for example, while using morpholine and triethylamine, the mol ratio of morpholine/triethylamine is generally more than 0.05, preferably more than 0.1, preferably more than 0.2, be generally below 20 further, preferably below 10, further preferably below 9.

It can add other template, but other templates are generally below 20% with respect to the mol ratio of integral mold plate agent, preferably below 10%.

Use the template in the present invention, can control the Si content in zeolite, can obtain as the preferred Si content of catalyst for cleaning up nitrogen oxides institute, Si existence.Its reason it be unclear that, but is presumed as follows.

For example, while synthesizing the SAPO of CHA type structure, for example morpholine of the ester ring type heterocyclic compound that contains hetero atom nitrogen can synthesize the SAPO that Si content is many with comparalive ease.But when the synthetic poor SAPO of Si, intensive composition or amorphous state composition are many, crystallization difficulty.In addition, for example triethylamine of alkylamine also can synthesize the SAPO of CHA structure under qualifications, but conventionally easily mixes the SAPO of various structures., easily form conversely speaking, the crystal structure without intensive composition or amorphous state composition.Namely, template separately has the feature of the crystallization that forms CHA structure, promote SAPO etc.We consider, by these features of combination, to bring into play synergism effect, have occurred independent irrealizable effect.

< carries out the synthetic > of zeolite by Hydrothermal Synthesis

Above-mentioned silicon atom raw material, aluminium atomic raw material, phosphorus atoms raw material, template and water are mixed to furnishing aqueous gel.Order by merging is unrestricted, suitably selects according to the condition using, and conventionally, first water is mixed with phosphorus atoms raw material, aluminium atomic raw material, then mixes with silicon atom raw material, template.

About the composition of aqueous gel, represent silicon atom raw material, aluminium atomic raw material and phosphorus atoms raw material, SiO by the mol ratio of oxide ₂/ Al ₂o ₃value be conventionally greater than 0, preferably more than 0.02, in addition, be generally below 0.5, preferably below 0.4, further preferably below 0.3.In addition, with same benchmark, P ₂o ₅/ Al ₂o ₃ratio be generally more than 0.6, preferably more than 0.7, preferably more than 0.8, be generally below 1.3, preferably below 1.2, further preferably below 1.1 further.

The composition of the zeolite obtaining by Hydrothermal Synthesis and the composition of aqueous gel are interrelated, in order to obtain having the zeolite of desired composition, suitably set the composition of aqueous gel.About the total amount of template, represent the aluminium atomic raw material in aqueous gel with oxide, template is with respect to Al ₂o ₃mol ratio be generally more than 0.2, preferably more than 0.5, preferably more than 1, be generally below 4, preferably below 3, further preferably below 2.5 further.

From every group of described two or more group, select more than one template, the order that this template is mixed is not particularly limited, can modulation template agent after, mix with other materials, also can respectively each template be mixed with other materials.

In addition, the ratio about water for aluminium atomic raw material, mol ratio is generally more than 3, preferably more than 5, preferably more than 10, is generally below 200, preferably below 150, further preferably below 120 further.

The pH of aqueous gel is generally more than 5, preferably more than 6, preferably more than 6.5, is generally below 10, preferably below 9, further preferably below 8.5 further.

In addition, in aqueous gel, also can contain above-mentioned composition in addition according to expecting.Such composition has the hydrophilic organic solvent of hydroxide or salt, the alcohol etc. of alkali metal or alkaline-earth metal for example.About the amount containing, the hydroxide of alkali metal or alkaline-earth metal or salt are generally below 0.2 with respect to the mol ratio of aluminium atomic raw material, and preferably, below 0.1, the hydrophilic organic solvent of alcohol etc. is generally below 0.5 with respect to the mol ratio of water, preferably below 0.3.

The aqueous gel obtaining is packed in pressure vessel, under self-generated pressure, or is not hindering under the gas pressurized of crystallization degree, stir or standing state under, the temperature stipulating by maintenance is carried out Hydrothermal Synthesis.The reaction temperature of Hydrothermal Synthesis is generally more than 100 ℃, preferably more than 120 ℃, preferably more than 150 ℃, is generally below 300 ℃, preferably below 250 ℃, further preferably below 220 ℃ further.In this temperature range, be up in the process of Da Wendu being warming up to maximum temperature, be preferably set to more than 1 hour, more preferably be set to more than 2 hours from the temperature province of 80 ℃ to 120 ℃.When the heating-up time less than 1 hour of this temperature range, there is inadequate situation in the durability of the obtained zeolite that contains template being fired to the zeolite obtaining.In addition,, from the viewpoint of durability, preferably the temperature range of 80 ℃ to 120 ℃ is arranged on 1 hour above further preferably more than 2 hours.

On the other hand, the upper limit of above-mentioned time is not particularly limited, long sometimes improper from the viewpoint of production efficiency, conventionally below 50 hours, from the viewpoint of production efficiency, preferably below 24 hours.

Temperature-rising method between described temperature province is not particularly limited, the various modes such as method and the mode that their combinations are carried out that can use method, the vibration etc. of for example simple method increasing, ladder variation to change up and down.Conventionally, consider from the easness of controlling, be applicable to adopting programming rate is remained on to the following mode heating up merely of certain value.

Also have, in the present invention, preferably near being up to Da Wendu, keep the stipulated time, be up to and refer near Da Wendu than the temperature of low 5 ℃ of this temperature to being up to Da Wendu, can affect the synthetic easness of desired thing being up to retention time under Da Wendu, therefore be generally more than 0.5 hour, preferably more than 3 hours, preferably more than 5 hours, be generally below 30 days further, preferably below 10 days, further preferably below 4 days.

The variations in temperature method that arrival is up to after Da Wendu is not particularly limited, and can use the method for stepped variation, be up to the various modes such as method and the mode that their combinations are carried out that change up and down such as vibrate below Da Wendu.Conventionally consider from the viewpoint of the durability of the easness of controlling, the zeolite that obtains, be up to after Da Wendu keeping, be advisable to cool to ambient temperature from 100 ℃.

The zeolite > that < contains template

Carry out hydro-thermal degree synthetic after, the zeolite that product is contained to template separates from hydrothermal synthesis reaction liquid, and the separation method of the zeolite that contains template is not particularly limited.Conventionally, can be by filtering or decant etc. separate, washing is dried at the temperature below room temperature to 150 ℃, obtains product.

Then, conventionally from the zeolite that contains template, remove template, its method is not particularly limited.Conventionally, under atmosphere by the inert gas containing air or oxygen or inert gas, at the temperature of 400 ℃ to 700 ℃, fire, or the method extracting etc. with ethanol water, containing the extractant of the ether of HCl etc., can remove the organic matter containing.From the viewpoint of manufacturing, preferably remove by firing.

In the manufacture of catalyst of the present invention, can on the zeolite of having removed template, hold metal, also can on the zeolite that contains template, hold after metal, remove again template, but few, easy from the viewpoint of manufacturing process, preferably on the zeolite that contains template, hold after metal, then remove template.

Hold metal on zeolite time, in the general ion-exchange process using, use and fire the zeolite of having removed template.This is because by having removed pore and the metal ion exchanged of template, and manufactures ion exchanged zeolite, and the zeolite that contains template is owing to can not carrying out ion-exchange, so be unsuitable for the manufacture of catalyst.In manufacture method of the present invention, by not carrying out ion-exchange, use the zeolite that contains template, from with the mixed dispersion liquid of metal remove decentralized medium, carry out following firing and the removing of template simultaneously, can manufacture catalyst, therefore be, favourable at manufacture view.

When removing the laggard row metal of template and holding, conventionally can remove by following the whole bag of tricks the template containing, under containing air or the inert gas of oxygen or the atmosphere of inert gas, conventionally the method for firing at the temperature more than 400 ℃, below 700 ℃, or the method extracting with ethanol water, containing extractants such as the ethers of HCl etc.

The metal that catalyst for removal of nitrogen oxide of the present invention can have by zeolite is carried with catalytic activity energy conventionally obtains.

< metal >

The metal using in the present invention is as long as holding on zeolite, and has the material of catalyst activity, is just not particularly limited, and is preferably selected from iron, cobalt, palladium, iridium, platinum, copper, silver, gold, cerium, lanthanum, praseodymium, titanium, zirconium etc.Further be preferably selected from iron or copper.In addition,, about the metal holding on zeolite, can combine and hold two or more metals.

In addition, in the present invention, " metal " may not refer in elementoid zeroth order state.Be called the situation of " metal ", comprise for example ionic or other existence of the existence that holding in catalyst.

There is no particular limitation for the source metal of the metal that the zeolite in the present invention holds, and can use slaine, metal complex, metal simple-substance, metal oxide etc., the acylate of inorganic acid salt or the acetate etc. of preferably nitrate, sulfate, hydrochloride etc.Source metal can solubilized or is insoluble to decentralized medium described later.

In the present invention, there is no particular limitation for the loading amount of the metal that uses, and is generally more than 0.1% with respect to the weight ratio of zeolite, preferably more than 0.5%, preferably more than 1%, is generally below 10%, preferably below 8%, further preferably below 5% further.Not enough described lower limit, has the less tendency of active site, and catalytic performance can manifest out.Exceed described higher limit, may exist the cohesion of metal to become significant tendency, catalytic performance reduces.

Catalyst used in the present invention also can with the reducing agent use that coexists.While wherein having coexisted reducing agent, can effectively carry out because purify, so preferably.Reducing agent can use ammonia, urea, organic amine, carbon monoxide, hydrocarbon, hydrogen etc., preferably uses ammonia, urea.

< catalyst for cleaning up nitrogen oxides >

Catalyst for cleaning up nitrogen oxides of the present invention, by electron probe microanalyzer (Electron microprobe analysis, is below referred to as EMPA), carries out element drawing, can observe the distribution under the electronics micro-dimension of this metal.This observational technique carries out conventionally as follows, catalyst fines is embedded in resin, after cutting with cross-sectional slice machine (diamond blade), at 10～50 μ m ²in scope, carry out the element drawing of metal, make the element spectrogram of 200 × 200 pixels.

Catalyst of the present invention is the Metal Distribution heterogeneity in zeolite normally, and a part of part exists metal, is preferably carried with more metal at catalyst surface.Particularly, in element drawing, the Metal Distribution heterogeneity in zeolite, can be by the intensity of the metal of EMPA the height of the coefficient of variation in figure represent, the coefficient of variation is more than 20%, preferably more than 25%.The coefficient of variation can be obtained divided by the mean value of whole pixels by the standard deviation of the metal strength of the whole pixels in element spectrogram.

When the ion-exchange using is in the ordinary course of things manufactured catalyst, have following supposition, because metal is distributed to comparably its crystals in zeolite, the lip-deep amount of metal of its actual zeolite crystal reacting is few, causes purifying property step-down.And the manufacture method of catalyst of the present invention is as long as making the inhomogenous method of Metal Distribution in zeolite, just be not particularly limited, preferably by modulation zeolite, the source metal of described metal and the mixture of decentralized medium, remove after decentralized medium, carry out holding of metal, we think, in this case, metal is distributed in zeolite surface unevenly, and the metal quantitative change that can make contributions to reaction is many, therefore purifying property is improved.The coefficient of variation of the metal in above-mentioned figure is below 20% time, is the state of metal equal dispersion in zeolite, therefore purifying property reduces.The upper limit is not particularly limited, and is generally below 100%, preferably below 50%.

The particle diameter of the metal in catalyst of the present invention can pass through transmission electron microscope (transmission electron microscope, below TEM) to be observed.

The particle diameter of the metal that catalyst of the present invention holds is not particularly limited, and more than this typically has a diameter from 0.5nm, below 20nm, preferred lower limit is more than 1nm, below the preferred 10nm of the upper limit, more preferably below 5nm.

While manufacture by the ion-exchange of general use, metal is dispersed in zeolite as ion differential, and this particle diameter is due to not enough 0.5nn, so can not observe with TEM.We think, directly purification is not made contributions, but the state of metal cohesion contribute to purification through the metal of ion-exchange.In addition, while using method of impregnation to be dried for a long time, observe metal cohesion, form the particle that is greater than 20nm.When metal is condensed into the particle that is greater than 20nm, the specific area of metal diminishes, and can contribute to the metal surface deficiency of reaction, and purifying property reduces.

About the observational technique of TEM, conventionally, after catalyst fines grinding dispersion is in ethanol, makes it dry and obtain sample, use this sample to observe.To the amount of sample, there is no particular limitation, but be preferably while carrying out tem observation, and the overlapping accumulation of zeolite intergranular is few, counts the degree in the visual field of a square photo of μ m specification but zeolite grain can enter into length and width again as much as possible.While observation with TEM like this, can on bright zeolite, observe the Cu particle of obfuscation.

The preferred 200kV to 800kV of accelerating potential when observation.During lower than 200kV, can not see through zeolite crystal, not observe the metallic holding, during higher than 800kV, can not obtain contrast, can not observe metallic.In addition, observation is to take pictures with high-sensitive CCD camera.Negative film is taken, narrow dynamic range, and metallic is black and not handy, likely can not observe metallic.

< ammonia TPD>

The ammonia adsorbance of catalyst of the present invention and adsorption strength can be measured by adopting the hot analytic method of ammonia (Temperature Progr ammed Desorption, hereinafter referred to as TPD method) to measure ammonia characterization of adsorption.

The peak temperature of catalyst of the present invention in ammonia TPD method is not particularly limited, preferably than hold by ion-exchange catalyst time high, be generally more than 250 ℃, preferably more than 280 ℃, be generally below 500 ℃, preferably below 350 ℃.

Catalyst of the present invention through ammonia TPD method measure ammonia adsorbance be not particularly limited, but more words, due to reduction amino-oxide reducing agent absorption increase, thereby preferably, more than being generally 0.6mol/kg, preferably more than 0.8mol/kg, more preferably more than 0.9mol/kg.The upper limit is not particularly limited, and is generally below 5mol/kg.

While making the metal of copper or iron etc. hold on zeolite, by these metal ions, hold on the acid position of zeolite.Therefore, more difficult at the acid position adsorb ammonia of zeolite that is carried with active metal, ammonia is faintly adsorbed on active metal.Therefore, the desorption temperature in ammonia TPD is low, conventionally has summit at 150～250 ℃., we think, when as catalyst for cleaning up nitrogen oxides, consider from the aspect of carrying out the reaction high SV, and preferably ammonia is more strongly adsorbed on catalyst.

Peak temperature and the ammonia adsorbance of ammonia TPD in catalyst of the present invention can be tried to achieve as follows.In order to remove adsorbed water, first under inert atmosphere, sample is warming up to 400～500 ℃, keep about 1 hour.Then, maintain 100 ℃ on one side, pass into ammonia on one side and adsorb for 15～30 minutes.The ammonium ion being adsorbed on the acid position of zeolite further forms ammonia with hydrogen bonding, in order to remove this ammonia, repeatedly proceeds as follows 5～10 times, imports steam, makes it to contact 5 minutes.After above-mentioned processing, under inert gas circulation, be warming up to 100～610 ℃ with the speed of 10 ℃/min, measure the ammonia amount of desorption at each temperature.Be the peak temperature of the peak of transverse axis while marking and drawing ammonia amount as ammonia TPD using getting temperature.In addition, using the total amount of the ammonia of desorption in temperature-rise period as ammonia adsorbance.

The 5th mode of catalyst of the present invention is characterised in that, at steam, repeatedly in adsorption desorption test, Adsorption Dimension holdup is more than 80%.

The steam that catalyst of the present invention is measured at 90 ℃ is repeatedly in adsorption desorption test, the preferably high person of Adsorption Dimension holdup, and Adsorption Dimension holdup is more than 80% conventionally, preferably more than 90%, more preferably more than 95%, the upper limit is 100%.In addition, steam repeatedly adsorption desorption test and the zeolite in the invention described above steam repeatedly adsorption desorption test identical.

Catalyst in the present invention, its carry out at 90 ℃ the steam measured repeatedly the water adsorption amount after adsorption desorption test be the water adsorption amount of 0.2 o'clock with respect to relative vapour pressure, preferably more than 70%, more preferably more than 80%, further preferably more than 90%.

In addition, this experimental condition is identical with the experimental condition of the zeolite in described the present invention.

That is, at 90 ℃, carry out 2000 steam adsorption desorption tests repeatedly, vapour pressure is the water adsorption amount of 0.2 o'clock being generally more than 70% before with respect to test relatively at 25 ℃ after test, preferably more than 80%, further preferably more than 90%.

The variation of the catalyst that catalyst of the present invention is caused by the adsorption desorption repeatedly of steam can be observed by the variation of the water vapor adsorption isotherms of the catalyst before and after test.

By repeatedly carrying out the adsorption desorption of water, the structure of catalyst does not have vicissitudinous words, and water vapor adsorption isotherms just can not change, and the structure of catalyst is damaged and waits variation, can observe adsorbance reduction.

The Adsorption Dimension holdup of adsorption desorption test is high repeatedly due to steam for catalyst of the present invention, the purification excellence of nitrogen oxide, and stability is high.We think, catalyst loading of the present invention is in enterprising enforcement used times such as automobiles, be actually the adsorption desorption that repeatedly carries out water, carry out purifying nitrogen oxide, therefore we think while repeatedly carrying out the repetition adsorption desorption of water not and can deteriorated catalyst to have the structure of waste gas purification ability excellence, have the detergent power of practical excellent nitrogen oxide.

<NO-IR>

Reaction intermediate during for the state of the metal existing in catalyst of the present invention and metal and reaction of nitrogen oxides, can have the infrared absorption spectroscopy (following, to be referred to as NO-IR) of nitric oxide production catalyst to observe by absorption.

Catalyst of the present invention is preferred, in the difference of the NO-IR before and after the catalyst absorption nitric oxide (NO) of 25 ℃ of mensuration, at 1860～1930cm ^-1between there is plural absorbing wavelength.

In addition, catalyst of the present invention is preferred, and the catalyst of measuring at 150 ℃ absorbs in the difference of the NO-IR before and after nitric oxide (NO), 1525～1757cm ^-1the maximum of peak intensity with respect to 1757～1990cm ^-1the ratio of maximum of peak intensity be below 1.

The high catalyst of purification of nitrogen oxides ability, except microdispersed metal ion, also comprises the metallic of the microcoacervation below the above 20nm of 0.5nm as above.Such particle at room temperature adsorbs nitric oxide production words, is adsorbed on respectively on metal ion and metal aggregated particle, at 1860～1930cm ^-1region in produce plural peak.In the zeolite of the catalyst of the ion-exchange manufacture by general use, be only carried with equably metal ion.When such catalyst at room temperature adsorbs nitric oxide, be adsorbed on nitric oxide on metal ion 1860～1930cm in NO-IR ^-1in region, only produce single absworption peak.But, such metal being held equably as single ionic, its purification of nitrogen oxides ability is little.1

Known, in nitrogen oxide, nitric oxide is more difficult to react.Therefore, first utilize catalyst to make oxidation of nitric oxide, generate nitrogen dioxide.The nitrogen dioxide generating reacts with nitric oxide, is decomposed into nitrogen and water.Due to nitric oxide and nitrogen dioxide 1757～1990cm in NO-IR respectively ^-1, 1525～1757cm ^-1observe, so can pass through NO-IR, the nitric oxide adsorbing in evaluate catalysts and the reactivity of nitrogen dioxide.

The reactivity of the nitrogen dioxide adsorbing on catalyst is low, even if improve temperature, the nitrogen dioxide on catalyst also can not be removed, so in NO-IR, in 1525～1757cm ^-1place observes strong peak.In NO-IR, 1525～1757cm ^-1peak little, represent nitrogen dioxide and nitric oxide fast reaction, remove from catalyst surface.

The NO-IR of catalyst of the present invention can measure as follows.

Room temperature measuring:

With in box, under vacuum, catalyst fines is warming up to 150 ℃ at determining adsorption, keeps 1 hour, using this as pre-treatment.Be cooled to 30 ℃, measure IR spectrum, spectrum as a setting.The NO that imports 20Pa, takes IR spectrum at any time.

150 ℃ of mensuration:

After room temperature measuring finishes, under vacuum, sample box is warming up to 150 ℃, keeps 1 hour, carry out pre-treatment.At 150 ℃, directly take IR spectrum, as a setting.The NO that imports 20Pa, takes IR spectrum at any time.

< electron spin resonance >

While being carried with copper in catalyst of the present invention, known by electron spin resonance (following ESR) spectrum, coordination structure and the character of metal ion and ligand binding etc. that part (such as oxygen) and copper (II) ion are obtained.

The distribution of the metal in catalyst of the present invention is inhomogenous.In such catalyst, there is two or more copper.For example, the copper etc. that has a size about 5～20nm through the copper of ion-exchange or microcoacervation is mingled in catalyst.Therefore, in ESR spectrum, have the catalyst of 2 above g|| factors that belong to copper (II) ion, its denitration activity is high and desirable.More preferably these two or more g|| get the value between 2.3 to 2.5.In the zeolite of the catalyst of manufacturing by the ion-exchange of general use, be only carried with equably a metal ion species.While measuring the ESR spectrum of such catalyst, have to belong to the g|| factor of copper (II) ion to one.But, such metal being held by homogeneous as single ionic, its purification of nitrogen oxides ability is little.

The ESR spectrum of catalyst of the present invention can be by following mensuration.

Catalyst fines 60mg is filled in the quartz ampoule of diameter 5mm, at 150 ℃, is dried tube sealing after 5 hours.After this coupon is arranged in ESR determinator, under the condition of magnetic field modulation 100kHz, response 0.1 second, field scan time 15min, microwave power 0.1mW, measure ESR spectrum.In addition, central magnetic field and scanning magnetic field width are arbitrarily.

The particle diameter of catalyst for cleaning up nitrogen oxides of the present invention is generally below 15 μ m, and preferably, below 10 μ m, lower limit is generally 0.1 μ m.As required, the dry type that can carry out jet pulverizer etc. is pulverized or the case of wet attrition of ball mill etc.In addition, the assay method of the assay method of the average grain diameter of catalyst and the particle diameter of above-mentioned zeolite is identical.

Catalyst for removal of nitrogen oxide of the present invention is preferred, when x-ray source uses CuK α to carry out XRD determining, except the peak from zeolite, is also that 21.2～21.6 degree are observed diffraction maximum in the angle of diffraction (20).There is diffraction maximum and refer to that, in the scope of the angle of diffraction 3～50 degree, the peak heights of 21.2～21.6 degree is more than 1% with respect to the peak heights of maximum intensity, preferably more than 2%, further preferably more than 5%.Peak heights refers to that the baseline that never has diffraction maximum is to the height of crest of peak.

The X-ray diffraction that is carried with the zeolite catalyst of metal is measured and can in the situation that catalyst not being processed, be carried out, and also can after it is heat-treated, carry out.While heat-treating, more than heat treatment temperature is generally 700 degree, preferably more than 750 degree, be generally below 1200 ℃, preferably below 1000 ℃, more preferably below 900 ℃.In addition, the heat treated time is generally more than 1 hour, preferably more than 2 hours, is generally below 100 hours, preferably below 24 hours.

" metal holds method "

While manufacturing catalyst of the present invention, metal species is held to method on zeolite, and there is no particular limitation, can use that the ion-exchange, the infiltration that generally use hold method, precipitation holds method, solid state ion exchange method, CVD method etc.Preferred ion exchange process, infiltration hold method.

The source metal of metal species is not particularly limited, and conventionally uses the salt of metal, for example, can use nitrate, sulfate, acetate, hydrochloride etc.

Infiltrate while holding, preferably, from pulpous state, be dried at short notice, more preferably use spray drying process to be dried.

After dry, conventionally heat-treat at 900 ℃ at 400 ℃.About heat treatment, in order to improve the dispersion of metal, improve the interaction of itself and zeolite surface, preferably heat-treat above at 700 ℃.Heat treated atmosphere is not particularly limited, and under atmosphere, under nitrogen, carry out under the inferior inert atmosphere of argon gas, can contain steam.

In addition, said heat treatment here refers to, the processing of steam treatment of carrying out when the physical property measurement of the catalyst for cleaning up nitrogen oxides of the invention described above etc., or described later while manufacturing catalyst for cleaning up nitrogen oxides of the present invention comprises the processing of firing.

Heat-treating methods is not particularly limited, and can use not (muffle) stove, kiln, the calcining furnace etc. that flows of horse, preferably passes into the method that above-mentioned gas is fired.The velocity of liquid assets of gas is not particularly limited, the circulation that is generally the gas of every 1g powder is under the circulation of 0.1ml/ minute above gas, heat-treat, the catalyst that obtains obtaining according to the present invention, preferably more than 5ml/ minute, be generally below 100ml/ minute, below preferably 20ml/ divides.

The circulation of the gas of every 1g powder is less than described lower limit, and acid residual in dry powder can not be removed in the time of heating, and zeolite may be destroyed, and circulation exceedes described higher limit above, and powder can disperse sometimes.

The heat treated temperature of carrying out in the present invention is not particularly limited, but conventionally can implement above at 250 ℃, preferably more than 500 ℃, is generally below 1000 ℃, preferably below 900 ℃.Less than described lower limit, source metal is not decomposed sometimes, exceedes described higher limit, and the structure of zeolite is likely destroyed.

The manufacture method of catalyst for cleaning up nitrogen oxides of the present invention is described above, it is characterized in that, from at least contain the zeolite of aluminium atom and phosphorus atoms or there is the zeolite of 8 ring structures and the mixture of source metal, decentralized medium, after removing the decentralized medium in mixture, fire, and carried out removing of described decentralized medium with 60 minutes following time.Below, describe manufacture method of the present invention in detail.

The manufacture method > of < catalyst for cleaning up nitrogen oxides

The manufacture method of catalyst for cleaning up nitrogen oxides of the present invention is described above, it is characterized in that, the mixture of modulation zeolite, metal and decentralized medium, removes the decentralized medium in described mixture, then fire, and carried out removing of described decentralized medium with 60 minutes following time.

The mixture > of < zeolite, source metal and decentralized medium

First, the mixture of modulation zeolite, source metal, decentralized medium (following, to be sometimes only referred to as mixture).

Decentralized medium in the present invention refers to the liquid for disperseing zeolite.The mixture using in the present invention is generally pulpous state or filter cake shape, but from the viewpoint of operational applicability, preferably pulpous state.

The kind of the decentralized medium using in the present invention is not particularly limited, but conventionally make water, alcohol, ketone etc., the viewpoint of the security during from heating considers, decentralized medium preferably makes water.

The order by merging of the mixture using in the present invention is not particularly limited, and conventionally, first makes source metal dissolve or be scattered in decentralized medium, and it is mixed with zeolite.The ratio that mixing mentioned component is modulated the solid constituent in the slurry forming is 5 quality %～60 quality %, preferably 10 quality %～50 quality %.The ratio of solid constituent is less than described lower limit, and the amount of the decentralized medium that should be removed is many, sometimes decentralized medium is removed to operation and causes obstacle.In addition, the ratio of solid constituent exceedes described higher limit, exists metal to be difficult to be dispersed in equably the tendency on zeolite.

The allotment temperature of the mixture using in the present invention is generally more than 0 ℃, preferably more than 10 ℃, common below 80 ℃, preferably below 60 ℃.

Conventionally, zeolite mixes with decentralized medium, heating sometimes, and allotment temperature exceedes described higher limit, and zeolite itself is likely because acid or alkali decompose.The lower limit of allotment temperature is the fusing point of decentralized medium.

The pH when allotment of the mixture using in the present invention is not particularly limited, and is generally more than 3, preferably more than 4, preferably more than 5, is generally below 10, preferably below 9, further preferably below 8 further.Allocate less than described lower limit or exceed higher limit in the situation that at PH, zeolite is likely destroyed.

Remove shape of particle, the particle diameter after decentralized medium for viscosity or the control of adjusting mixture, in the mixture that can use in the present invention, add various additives.The kind of additive is not particularly limited, preferably inorganic additive, and having for example inorganic sol, clay is additive etc.Inorganic sol uses silicon dioxide gel, alumina sol, TiO 2 sol etc., preferably silicon dioxide gel.The average grain diameter of inorganic sol is 4～60nm, preferably 10～40nm.Clay is that additive uses sepiolite, montmorillonite, kaolin etc.

The addition of additive is not particularly limited, but its weight ratio with respect to zeolite is below 50%, preferably below 20%, further preferably below 10%.Weight ratio exceedes described higher limit, the situation that exists catalyst performance to reduce.

The method of the mixed method of the mixture using in the present invention as long as making zeolite and source metal mix fully or disperse, can be used various known methods, specifically can use stirring, ultrasonic wave, homogenizer etc.

< decentralized medium remove >

Then in the mixture, using, remove decentralized medium from the present invention.The method of removing of decentralized medium is as long as removing at short notice the just special restriction of nothing of method of decentralized medium, the method of preferably removing at short notice through the state of homogeneous spraying, more preferably make it to contact with high temperature thermal medium and the method for removing through the state of homogeneous spraying, further preferably by making it to remove with contacting to be dried as the hot blast of high temperature thermal medium through the state of homogeneous spraying, obtain the method for homogeneous powder, i.e. " spraying is dry ".

When application spraying is in the present invention dry, spray method can use the centrifugal spray by rotating circular disk, by the pressure atomization of drive nozzle, and the spraying by second fluid nozzle, four fluid tips etc. etc.

The slurry of spraying, by contacting with the thermal medium such as metallic plate or high-temperature gas heating, is removed decentralized medium.The temperature of the hot media in which kind of situation is all not particularly limited, more than being generally 80 ℃, below 350 ℃.Less than described lower limit, sometimes can not from slurry, remove fully decentralized medium, in addition, exceed described higher limit, source metal is decomposed sometimes, metal oxide cohesion.

While using spraying dry, this drying condition being not particularly limited, is that about 200～300 ℃, gas outlet temperature are set as about 60～200 ℃ and implement conventionally by gas access Temperature Setting.

In the present invention, from mixture, removing the required time of decentralized medium refers to that the amount of the decentralized medium in mixture arrives the required time below 1 quality %, refer to that from the temperature of mixture be the more than 80 ℃ moment drying time when decentralized medium is water, the amount of the water containing to mixture accounts for the time below 1 quality % in the mixture obtaining.Decentralized medium is to refer to that the amount of the decentralized medium containing to mixture accounts for the time below 1 quality % in the mixture obtaining from becoming the moment in the temperature of low 20 ℃ of the boiling point normal pressure than this decentralized medium the drying time outside water time.The time of removing of decentralized medium is below 60 minutes, preferably below 10 minutes, more preferably below 1 minute, further preferably below 10 seconds because wish at shorter time inner drying, thus lower limit be not particularly limited, but conventionally more than 0.1 second.

The time that cost exceedes described higher limit is removed decentralized medium from mixture, and source metal can be condensed, held on the surface of zeolite that holds metal to heterogeneity, and becomes the reason that catalyst activity reduces.In addition, we think, common metal source, owing to being acid or alkaline, so under the existence of decentralized medium, under the state that contains these metals, be exposed to for a long time under hot conditions, can promote the structure of the zeolite that holds metallic atom to decompose.Therefore can think that drying time is longer, the activity of catalyst is just lower.

In addition, there is no particular limitation to remove the average grain diameter of the dry powder obtaining after decentralized medium, is generally below 1mm, preferably below 200 μ m, more than common 2 μ m, removes decentralized medium to can complete at short notice dry.

< fires >

By firing removing the dry powder obtaining after decentralized medium, obtain catalyst of the present invention.Method for cooking is not particularly limited, and can use not (muffle) stove of horse, kiln, the baking furnace etc. of flowing, but preferably pass into that gas fires according to the method for acquisition catalyst of the present invention.The velocity of liquid assets of gas is not particularly limited, and the circulation of the gas of common every 1g powder is more than 0.1ml/ minute, preferably more than 5ml/ minute, is generally below 100ml/ minute, preferably below 20ml/ minute.By firing, obtain catalyst of the present invention under described gas communication.The circulation of the gas of every 1g powder is less than described lower limit, and acid residual in dry powder can not be removed in the time of heating, and zeolite may be destroyed, and circulation exceedes described higher limit, and powder can disperse sometimes.

There is no particular limitation for circulated gases, can use air, nitrogen, oxygen, helium, argon gas or their mist etc., preferably uses air.In addition, circulated gases can contain steam.Also can use the method for firing under reducing atmosphere, now, can in gas, mix hydrogen, or in catalyst, mix the organic matters such as oxalic acid and fire.

The temperature of firing of carrying out in the present invention is not particularly limited, but conventionally can implement above at 250 ℃, preferably more than 500 ℃, is generally below 1000 ℃, preferably below 900 ℃.Less than described lower limit, source metal is not decomposed sometimes, exceedes described higher limit, and the structure of zeolite is likely destroyed.

Firing time is 1 second～24 hours, preferably 10 seconds～8 hours, and preferably 30 minutes～4 hours further.In addition, after firing, also catalyst can be pulverized.

" zeolite "

The zeolite that the zeolite that the present invention uses can use skeleton to contain silicon atom, aluminium atom, phosphorus atoms.

In addition, the skeletal density of mesolite of the present invention is the parameter of reflection crystal structure, is not particularly limited, and IZA, for the numerical value that ATLA S OF ZEOLITE FRAMEWORK TYPES Fifth Revised Edition2001 records, it typically is

above, preferred

above.

In addition be generally,

below, preferred

below.Preferred further

below.

< catalyst mixture >

The catalyst that contains zeolite of the present invention can be directly with Powdered use, also can mix with adhesive such as silica, aluminium oxide, clay minerals, after making the mixture (following, to be sometimes referred to as catalyst mixture) that contains catalyst, use.

In addition,, in order to improve formability or intensity, in the scope that can not make its performance reduce, can add various materials.Specifically can add the clay mineral classes such as the inorfil such as alumina fibre, glass fibre class, sepiolite etc., the inorfil classes such as preferential oxidation aluminum fiber, glass fibre.

< adhesive >

In described catalyst mixture, contained adhesive is generally inorganic adhesive or the organic adhesion agent of clay mineral classes such as silica, aluminium oxide, sepiolite etc., in addition, also can be polysiloxane-based, silicic acid liquid, specific silicon dioxide gel or alumina sol etc., carry out modification or reaction by crosslinked bonding etc., and performance is as the material (following, to be sometimes referred to as adhesive presoma) of adhesive function.

, polysiloxane-basedly refer to that main chain has oligomer or the polymer of polysiloxanes key here, a substituent part that also comprises the main chain of polysiloxanes key is hydrolyzed and forms the material of 0H base.Condensation reaction is carried out in cryogenic temperature region polysiloxane-based, silicic acid liquid ℃ left and right in room temperature～300.In addition, " specific silica gel " refers to the silica gel that carries out condensation reaction in above-mentioned temperature province.

Consider from the easness being shaped, in described catalyst mixture, contained adhesive is preferably brought into play polysiloxane-based, the silicic acid liquid of adhesive function, specific silicon dioxide gel or alumina sol etc. and composition thereof by be cross-linked the modifications such as bonding or reaction in the processes such as mixing, the viewpoint of the intensity during from following shaping is considered, more preferably polysiloxane-based, silicic acid liquid and composition thereof, the compound shown in preferred formula (I) or silicic acid liquid and composition thereof further.

[changing 2]

(wherein, in formula (I), R is can substituted alkyl independently of one another, aryl, and alkenyl, alkynyl, alkoxyl or phenoxy group, R ' is independent is separately can substituted alkyl, aryl, alkenyl or alkynyl, n is 1 to 100 number.〕

R preferable examples has the alkyl of carbon number 1～6, the aryl of carbon number 6～12, the alkenyl of carbon number 2～6, alkynyl, the alkoxyl of carbon number 1～6 or the aryloxy group of carbon number 6～12 of carbon number 2～6, and they can be substituted arbitrarily.Further preferably there are for example independently of one another non-substituted alkoxyl, alkyl, aryloxy group, particularly preferably alkoxyl, wherein preferred ethyoxyl or methoxyl group, most preferably methoxyl group.

The alkyl of the preferred carbon number 1～6 of R ', aryl, the alkenyl of carbon number 2～6 or the alkynyl of carbon number 2～6 of carbon number 6～12, these can replace arbitrarily.The preferably alkyl of non-substituted carbon number 1～5, preferable methyl or ethyl further, most preferable.

The hydrolysate of above-mentioned formula (I) part is R, and at least a portion of R ' is by being hydrolyzed the material becoming after OH base.Repetitive n is generally 2～100, and preferably 2～50, further preferably 3～30.

According to the value of n, the compound of formula (I) here can be with the form of the form of monomer or long-chain, exist containing the form of side chain arbitrarily.

Polysiloxane-based usual methyl silicate, the such alkyl silicate of silester of containing that the present invention uses.

In addition, the silicic acid liquid in the present invention is from silicate base solution, to remove the material after alkali metal ion.The method of removing of alkali metal ion is not particularly limited, and for example, can adopt the known method of ion-exchange etc., for example, as described in No. 3540040 communique of Japan Patent, Japanese Patent Laid-Open 2003-26417 communique, sodium silicate solution is contacted with the cationic ion-exchange resin of H+ type, modulate.Silicate base, except sodium metasilicate, can also use potassium silicate or their mixture, considers, preferably sodium metasilicate from the viewpoint of the easness of starting with.About H+ type cationic ion-exchange resin, by commercially available crystalline substance such as ダィァィオ Application SKT-20L (society of Mitsubishi Chemical system), ァ Application バ mono-ラィト IR-120B (society of Mitsubishi Chemical system) etc. become H+ type by common method ion-exchange after use.The requirement of cationic ion-exchange resin using is selected according to known understanding, but normally can obtain at least with silicate base in the amount of the equal or above cation exchange capacity of alkali metal ion amount.Ion-exchange can be flow type, step any one, conventionally adopt flow type.

SiO in silicic acid liquid ₂concentration is not particularly limited, and is generally 1～10 quality %, the intensity during from the viewpoint of following shaping, preferably 2～8 quality %.In silicic acid liquid, can contain the stabilizing agent of the organic base of a small amount of alkali metal ion, organic amine, quaternary ammonium and so on.The concentration of these stabilizing agents is not particularly limited, and enumerates as an example of alkali metal ion example, and the concentration in silicic acid liquid is generally below 1 quality %, consider from adsorption capacity, and preferably below 0.2 % by weight, particularly preferably 0.0005～0.15 quality %.

About the control of alkali metal ion concentration, can in the silicic acid liquid of removing alkali metal ion, add the soluble-salts such as alkali metal hydroxide, hydroxide, sodium metasilicate until its below about 100ppm, alkali metal ion concentration that also can be residual according to the control of ion-exchange condition.

< formed body >

Catalyst for cleaning up nitrogen oxides of the present invention or catalyst mixture also can granulation or rear uses that be shaped.

The method of granulation or shaping is not particularly limited, and can adopt various known methods to carry out.Conventionally, described catalyst mixture is shaped, uses as formed body.The shape of formed body is preferably used cellular.

In addition,, when the exhaust gas catalyst used etc. as automobile, the method for shaping is used coating process or forming process, makes honeycombed catalyst.While adopting coating process, conventionally, catalyst for cleaning up nitrogen oxides of the present invention is mixed with the inorganic adhesive such as silica, aluminium oxide, make pulping, be coated in again the surface of the cellular thing of the inorganic matter making such as cordierite, fired, be made thus.While adopting forming process, conventionally, by mixing the inorfils such as inorganic adhesive or alumina fibre, glass fibre such as catalyst for cleaning up nitrogen oxides of the present invention and silica, aluminium oxide, carry out the shaping of extrusion molding or compression method etc., proceed to fire, obtain thus preferred cellular catalyst.

In addition, obtain after formed body, can be by adhesive applicating be strengthened to formed body on surface.Now, adhesive can use above-mentioned adhesive arbitrarily, and the viewpoint consideration of the intensity during from following shaping is more preferably polysiloxane-based, silicic acid liquid and composition thereof, the further compound shown in preferred formula (I) or silicic acid liquid and composition thereof.

Formed body of the present invention is preferably manufactured by the operation that contains following three operations.

(1) the 1st operation, mixes the inorfil of described catalyst for cleaning up nitrogen oxides and alumina fibre, glass fibre etc. and adhesive, modulation catalyst mixture,

(2) the 2nd operations, the catalyst mixture extrusion molding that the 1st operation is obtained, obtains formed body presoma,

(3) the 3rd operations are fired the formed body presoma that the 2nd operation obtains in the scope of 150 ℃ to 800 ℃.

(the 1st operation)

In the 1st operation, mix to the inorfils such as major general's catalyst for cleaning up nitrogen oxides and alumina fibre, glass fibre and adhesive, be modulated into catalyst mixture.

Catalyst for cleaning up nitrogen oxides in catalyst mixture and the mixed proportion of adhesive are normally, adhesive is with respect to catalyst for cleaning up nitrogen oxides 100 weight portions, be converted into the words of oxide, be 2～40 weight portions, from the viewpoint of balance strength and catalytic performance, preferably use with the ratio of 5～30 weight portions.

In addition mixing water in catalyst mixture conventionally.Its mixed proportion is also determined by forming method, conventionally, is 10～500 weight portions with respect to catalyst for cleaning up nitrogen oxides.For example, when extrusion molding, be 10～50 weight portions with respect to catalyst for cleaning up nitrogen oxides, preferably 10～30 weight portions.In addition,, according to mixing, characteristic while extruding in the second operation, for the object that improves mobility, can in this catalyst mixture, add the cellulose families such as methylcellulose, starch, the plasticizer such as polyvinyl alcohol.Its mixed proportion is 0.1～5 weight portion with respect to catalyst for cleaning up nitrogen oxides 100 weight portions, from the viewpoint of intensity, and preferably 0.5～2 weight portion.

(the 2nd operation)

In the 2nd operation, by the catalyst mixture extrusion molding obtaining in the 1st operation, obtain formed body presoma.

The device that extrusion molding is used can use known extrusion shaping machine.Conventionally, add catalyst for cleaning up nitrogen oxides, inorfil, adhesive, water and plasticizer as required, carry out mixingly, then carry out moulding with extrusion shaping machine.Pressure when moulding is not particularly limited, but is generally 5～500kgf/cm ²left and right.After granulation, conventionally, be dried to the temperature of 150 ℃ of left and right at 50 ℃, obtain target formed body presoma.

(the 3rd operation)

In the 3rd operation, at the temperature within the scope of 150 ℃ to 900 ℃, fire the formed body presoma that the 2nd operation obtains.This temperature is preferably more than 200 ℃, further preferably more than 250 ℃, particularly preferably more than 300 ℃, conventionally preferably below 800 ℃, further preferably below 700 ℃.By firing in said temperature scope, reach in fact the crosslinked bonding of adhesive presoma, obtain high-intensity formed body.

Catalyst for cleaning up nitrogen oxides of the present invention is contacted with the waste gas that contains nitrogen oxide, can purifying nitrogen oxide.About the contact conditions of catalyst for cleaning up nitrogen oxides and waste gas, generally more than space velocity 100/h, use, more than 1000/h, be preferably below 500000/h in addition, preferably below 100000/h.In addition, serviceability temperature is more than 100 ℃, preferably more than 150 ℃, also below 700 ℃, preferably below 500 ℃.

The using method > of < catalyst

The catalyst that contains zeolite using in the present invention can be directly in Powdered lower use, also can mix with the adhesive such as silica, aluminium oxide, clay mineral, carry out granulation or be shaped after use.In addition, while being used as the exhaust gas catalyst that automobile uses etc., can adopt coating process or forming process to form rear use, be preferably shaped to cellular rear use.

The catalyst mouldings obtaining according to the present invention is (following by coating process manufacture, sometimes be only referred to as element) time, conventionally, the inorganic adhesive such as zeolite catalyst and silica, aluminium oxide is mixed, make pulping, then the inorganic matters such as cordierite are coated on the surface of formed body of making, fire and form, now, preferably by being coated on the formed body of honeycomb shape, obtain cellular catalyst.

The catalyst mouldings obtaining according to the present invention is in the time manufacturing by forming process, conventionally, by mixing the inorfil such as inorganic adhesive or alumina fibre, glass fibre of zeolite and silica, aluminium oxide etc., via the shaping of extrusion molding or compression method etc., continue to fire and form, now preferably by being configured as the cellular cellular element that obtains.

Catalyst in the present invention is by contacting purifying nitrogen oxide with the waste gas that contains nitrogen oxide.This waste gas can comprise the composition beyond nitrogen oxide, for example, can comprise hydrocarbon, carbon monoxide, carbon dioxide, hydrogen, nitrogen, oxygen, sulfur oxide, water.Particularly, use method of the present invention, can purify the contained nitrogen oxide of various waste gas of discharging the various Diesel engines used from diesel car, gasoline automobile, stationary power generation boats and ships-agricultural machinery-construction implement-cart aviation machine, boiler, gas turbine etc.

While using the catalyst in the present invention, the contact conditions of catalyst and waste gas is not particularly limited, more than being generally space velocity 100/h, preferably more than 1000/h, conventionally below 500000/h, preferably below 100000/h, temperature is generally more than 100 ℃, preferably more than 150 ℃, common below 700 ℃, preferably below 500 ℃.

Come in the back segment operation of purifying nitrogen oxide at the catalyst for purification of nitrogen oxides of using with the present invention, by loading the catalyst that can be oxidized the residue reducing agent not being consumed in purifying nitrogen oxide, can reduce the reducing agent in waste gas.Now, oxidation catalyst can use for catalyst adsorbent-reductant, be carried with the metals such as platinum family on the carriers such as zeolite, and this zeolite and oxidation catalyst can use zeolite of the present invention and catalyst.

Embodiment

Below, by embodiment, the present invention is carried out to further description, but the present invention is not limited by following embodiment.

< embodiment 1A～3A, comparative example 1A～5A>

The embodiment of the 1st～4th mode of the present invention is as follows.

(assay method of XRD)

X-ray source: Cu-K alpha ray

Power setting: 40kV30mA

Optical condition when mensuration:

Divergent slit=1 °

Scatter slit=1 °

Be subject to optical slits=0.2mm

The position of diffraction maximum: 2 θ (angle of diffraction)

Measurement range: 2 θ=3～50 degree

Sweep speed: 3.0 ° (2 θ/sec), continuous sweep

The modulation of sample: for the artificial about 100mg of sample pulverizing of agate mortar, adopt the specimen holder Sheng of same shape to get quantitative sample.

(method of constituent analysis)

After sample alkali is dissolved, carry out acid-soluble solution, obtain a solution, analyze this solution by inductively coupled plasma luminescence analysis (ICP-AES method).

(assay method of TEM)

The method of making sample is as follows: in mortar, pack ethanol and catalyst fines into, grind after about 10 minutes, use supersonic wave cleaning machine, make it to be dispersed in ethanol, place after several minutes, drip in right amount in being coated with carbon film (specification 15nm below) finely on the net, make it natural drying.

Tem observation condition

Device: the H-9000UHR processed of Hitachi (existing, Ha ィテタノロジ mono-ズ of Hitachi)

Accelerating potential: 300kV adjusts under the condition that can obtain high-definition picture

Take a picture: the high-sensitive CCD camera AMT Advantage HR-B200 of society

Under these conditions, at least observe the zeolite crystal in 3500 squares of μ m regions.

(assay method of electron probe microanalyzer EMPA)

As pre-treatment, catalyst fines is embedded in resin, after cutting with cross-sectional slice machine (diamond blade), carry out Au evaporation.

Device: the JXA-8100 processed of JEOL society

Electron gun: W emitter stage, accelerating potential 15kV, irradiates electric current 20nA

Element drawing: analyze area 15.6 μ m ²(be equivalent to × 5000), acquisition time 200msec/point,

Object elements (analyzing crystal) Si (PET), Cu (LIFH)

(ammonia TPD)

Device: Japanese ベ Le society TP5000 type processed

Sample size: 30mg

Use gas: carrier gas He, adsorbed gas 5%NH3/He

Pre-treatment: under the condition of He50ml/min, sample is warming up to 450 ℃, keeps 1 hour, be cooled to 100 ℃.

Ammonia absorption: maintaining in 100 ℃, in 5%NH ₃under the condition of/He50ml/ minute, adsorb 15 minutes.

Steam treatment: repeatedly proceed as follows 7 times, after vacuumizing, steam is imported in system, make it to contact 5 minutes, then vacuumize.

Desorption is measured: under the condition of dividing at He50ml/, be warming up to 610 ℃ with 10 ℃/point from 100 ℃.

< steam adsorption desorption test repeatedly (" the repeated durability test of 90-80-5 ") >

Steam repeatedly adsorption desorption test is repeatedly to proceed as follows: sample is remained in the vacuum tank that maintains 90 ℃, expose 90 seconds kinds respectively under the saturated steam atmosphere of 5 ℃ He under 80 ℃ of saturated steam atmosphere.Now, under the saturated steam atmosphere of 5 ℃, the part generation desorption of the water that sample adsorbs while being exposed to the saturated steam atmosphere of 80 ℃, moves to the tank that maintains 5 ℃.The total amount (Qn:m (g)) of the water being moved by the tank to 5 ℃ being adsorbed onto the n time desorption from the m time and the dry weight (W (g)) of sample, obtain each average adsorbance (Cn:m (g/g)) by following formula.

[Cn：m]＝[Qn：m]／(n-m+1)／W

Conventionally, absorption, desorption carry out more than 1000 times repeatedly, and preferably more than 2000 times, the upper limit is not particularly limited.

(above operation being called to " steam of measuring at 90 ℃ adsorption desorption test repeatedly ")

(NO-IR)

Determinator: Japanese light splitting society FT-IR6200FV type processed

Detector: MCT

Resolution: 4cm-1

Cumulative number: 256 times

Sample size: approximately 5mg

Use gas: 10%NO/He

Sampling: directly sample is coated on the CaF plate of rough lapping under atmosphere, encloses in determining adsorption box.

Pre-treatment (normal temperature): under vacuum, sample is warming up to 150 ℃ at determining adsorption in box, keeps 1 hour, carry out pre-treatment, then cool to 30 ℃.Now, take spectrum, as a setting.

NO adsorbs (normal temperature): carry out after described pre-treatment (normal temperature), according to the manometric indication in vacuum line, import the NO of 20Pa, take at any time IR spectrum.

Pre-treatment (150 ℃): carry out after described NO absorption (normal temperature), under vacuum, sample is warming up to 150 ℃ at determining adsorption in box, keep 1 hour, carry out pre-treatment, directly maintain 150 ℃.Now, take spectrum, as a setting.

NO adsorbs (150 ℃): according to the manometric indication in vacuum line, import the NO of 20Pa, take at any time IR spectrum.

(ESR)

Determinator: the FA300 processed of JEOL society

Condition determination: central magnetic field is any

Scanning magnetic field width is any

Magnetic field modulation 100kHz

Respond 0-1 second

Field scan time 15min

Microwave power 0.1mW

Catalyst fines sample 60mg is filled in the quartz ampoule of diameter 5mm, at 150 ℃, is dried tube sealing after 5 hours.

(evaluation method of catalyst activity)

The catalyst of modulation is according to following its catalytic activity of method evaluation.

Catalytic evaluation 1

By after the catalyst punch forming of modulation, to break into pieces, whole grain becomes 16～28 orders.Each catalyst 5ml that whole grain is crossed is filled in atmospheric fixed bed flow type reaction tube.With 2900ml/min (space velocity SV=35000/h), the gas of the composition of table 1 is circulated on catalyst layer, catalyst layer is heated simultaneously.At the temperature of 150 ℃, 175 ℃, when fixing according to outlet NO concentration, the value of following formula is carried out the nitrogen oxide of evaluate catalysts except deactivation respectively.

(NO purifying rate)={ (entrance NO concentration)-(outlet NO concentration) }/(entrance NO concentration)

Catalytic evaluation 2

Catalytic amount is decided to be to 1ml, with space velocity SV=100000/h circulation, in addition, adopts the evaluation method equal with evaluating catalyst 1, nitrogen oxide is removed to deactivation and evaluate.

[table 1]

Gas componant	Concentration
		NO	350ppm
NH ₃	385ppm
		O ₂	15 volume %
H
	₂0	5 volume %
N ₂			The remainder of mentioned component

(embodiment 1A)

According to the disclosed method of embodiment 2 of Japanese Patent Laid-Open 2003-183020 communique, synthesized silicon-aluminum phosphate zeolite.The zeolite obtaining, through XRD determining, is CHA structure

in addition, in the time that icp analysis carries out the composition analysis of zeolite, the each composition of result is with respect to the composition (mol ratio) of the total of silicon, aluminium and the phosphorus of skeleton structure, and silicon is 0.092, and aluminium is 0.50, and phosphorus is 0.40.

Then, in copper acetate (II) monohydrate (キシダ chemistry society system) of 9.4g, add the pure water of 200g, make it to dissolve, add the above-mentioned zeolite of 100g, further stir, make water slurry.The water slurry of this normal temperature is sprayed on 170 ℃ of metallic plates, makes it dry, make catalyst precursor.The dry needed time is below 10 seconds.In the circulation of air of 12ml/ minute of every 1g catalyst, at 500 ℃, fire catalyst precursor 4 hours, obtain catalyst l.For catalyst 1, according to the condition of above-mentioned

catalytic evaluation

1 and 2, evaluate NO purifying rate.Catalytic evaluation 1 the results are shown in table 2, catalytic evaluation 2 the results are shown in table 3.In addition, the ammonia TPD of catalyst 1 after measured, summit is 321 ℃.In addition, the ammonia adsorbance of catalyst 1 is 1.1mol/kg.

(embodiment 2A)

Copper acetate (II) monohydrate (キッダ chemistry society system) of zeolite 2kg, the 188g that embodiment 1A is recorded, 3266g pure water stir, and make water slurry.Adopt the water slurry of dry this normal temperature of disc rotary type spray dryer of 1200 Φ.Drying condition is that inlet temperature is set as 200 ℃, and outlet temperature is set as 120 ℃.The speed setting of disk is 18000rpm.Supply with slurry with the speed of 1.5kg/ hour, with the dry powder that reclaims 577g for 1 hour.The dry needed time is below 10 seconds.Similarly fire this dry powder with embodiment 1A, obtain catalyst 2.For catalyst 2, the same with embodiment 1A, the condition of employing catalytic evaluation 1, evaluates NO purifying rate.Result is shown in table 2.In addition, under the condition of catalytic evaluation 2, evaluate NO purifying rate.Result is shown in table 3.

The TEM image of this catalyst 2, observes as shown in Figure 1 after measured, and the copper particle of 1～3nm is dispersed on zeolite.Under the atmosphere that contains 10% steam, at 800 ℃, catalyst 2 was carried out to steam treatment after 5 hours, TEM image equally after measured, observes as shown in Figure 2, and the copper particle of 1～3nm is dispersed on zeolite.

This catalyst 2 is embedded in resin, and with after the cutting of cross-sectional slice machine, EPMA after measured, obtains element drawing, as shown in Figure 3 known, even in the place of observing the Si in zeolite, also has and detects the higher part in Cu part and low-down part.The coefficient of variation of trying to achieve the Cu strength ratio of each pixel of 200 × 200 is 33%.

In addition, the ammonia TPD of catalyst 2 after measured, summit is 306 ℃.In addition, the ammonia adsorbance of catalyst 2 is 1.1mol/kg.

The NO-IR of catalyst 2 after measured, result is at room temperature, 1860～1930c ^m-1 regional observation is to 1886cm ^-1and 1904cm ^-1two peaks.In addition, at 150 ℃, 1525～1757cm ^-1peak intensity with respect to 1757～1990cm ^-1peak intensity be 0.1.

The ESR spectrum of catalyst 2 after measured, result is to observe two kinds of copper (II) ion of two values with g||=2.38 and g||=2.33.

(embodiment 3A)

According to the disclosed method of embodiment 2 of Japanese Patent Laid-Open 2003-183020 communique, the synthetic SAPO zeolite that contains template.SAPO zeolite contains the template of totally 20 % by weight.The pure water that adds 200g in copper acetate (II) monohydrate (キシダ chemistry society system) of 9.4g, makes it to dissolve, and adds the above-mentioned zeolite of 100g, then stirs, and makes water slurry.The water slurry of this normal temperature is sprayed on 170 ℃ of metallic plates, makes it dry, make catalyst precursor.The dry needed time is below 10 seconds.In the circulation of air of 12ml/ minute of every 1g catalyst, at 700 ℃, catalyst precursor is fired 2 hours, remove template simultaneously, obtain catalyst 7.With the NO purifying rate of the condition evaluating catalyst 7 of catalytic evaluation 2.Result is shown in table 3.

(embodiment 4A)

In water, add verdigris (II) (キシダ chemistry society system) 1.1g and pure water 40g as insoluble Cu source, make aqueous dispersions, add the zeolite 20g using in embodiment 2A, then stir, make water slurry.The water slurry of this normal temperature is sprayed on 170 ℃ of metallic plates, makes it dry, make catalyst precursor.The dry needed time is below 10 seconds.

Under the condition in the circulation of air of 12ml/ minute for every 1g catalyst, at 850 ℃, catalyst precursor is fired 2 hours, obtain catalyst 9.

(embodiment 5A)

Except implement dried the firing 2 hours of spraying in the rotary furnace of 750 ℃, other use the method same with embodiment 2A, obtain catalyst 10.

The NO-IR of catalyst 10 after measured, result is, at room temperature, at 1860～1930cm ^-1regional observation to 1886cm ^-1and 1904cm ^-1two peaks.In addition, at 150 ℃, 1525～1757cm ^-1peak intensity with respect to 1757～1990cm ^-1peak intensity be 0.1.

The ESR spectrum of catalyst 10 after measured, result is to observe two kinds of copper (II) ion of two values with g||=2.38 and g||=2.33.

(comparative example 1A)

In the zeolite of embodiment 1A, add copper acetate (II) aqueous solution of 5.9 quality %, make pulping, make after filtration filter cake shape.The pulverizing limit, filter cake limit obtaining at 100 ℃ is dry.Be 2 hours drying time.Then, similarly fire dry powder with embodiment 1A, obtain catalyst 3.For catalyst 3, the same with embodiment 1A, the condition of employing catalytic evaluation 1, evaluates NO purifying rate.The results are shown in table 2.

(comparative example 2A)

Use 8.9 quality % copper nitrate (II) aqueous solution to soak, make to be carried with on the zeolite of embodiment 1A the copper of 3 quality %, at 100 ℃, after being dried with drying machine, similarly fire with embodiment 1A, obtain catalyst 4.Be 24 hours drying time.For catalyst 4, the same with embodiment 1A, the condition evaluating NO purifying rate of employing catalytic evaluation 1.The results are shown in table 2.

(comparative example 3A)

In the zeolite of embodiment 1A, add 5.9 quality % copper acetate (II) aqueous solution, be heated to 60 ℃, stir after 4 hours, through filtering, clean, ion-exchange is carried with copper (II) ion.After dry with drying machine at 100 ℃, similarly fire with embodiment 1A, obtain catalyst 5.Be 24 hours drying time.For catalyst 5, the same with embodiment 1A, the condition of employing catalytic evaluation 1, evaluates NO purifying rate.The results are shown in table 2.

(comparative example 4A)

In the zeolite of embodiment 1A, add copper acetate (II) aqueous solution of 5.9 quality %, make pulping, make after filtration filter cake shape.At 85 ℃, the pulverizing limit, filter cake limit obtaining is dry.Be 2 hours drying time.Then, in the Muffle furnace of 500 ℃, will be dried powder and fire 4 hours, obtain catalyst 6.For catalyst 6, the same with embodiment 1A, the condition of employing catalytic evaluation 1, evaluates NO purifying rate.The results are shown in table 2.

(comparative example 5A)

In water 188g, add 85% phosphoric acid 80.7g, then add the boehmite (Pural SB, Condea system, 75%Al203) of 54.4g, stir 2 hours.In this mixture, add after aerosil (ァエロジ Le 200) 6.0g, then add 35%TEAOH (tetraethyl ammonium hydroxide) aqueous solution 336.6g, stir 2 hours.This mixture is packed in the stainless steel autoclave of 1L of fluororesin inner core, under the stirring of 150rpm rotating speed, in 190 ℃ of reactions 24 hours.After reaction, adopt the method identical with embodiment 1A to obtain zeolite.CHA structure through this zeolite of XRD determining.In addition, with respect to the total of aluminium, phosphorus and the silicon of skeleton structure, the composition (mol ratio) of each composition through the result of elementary analysis be that silicon is 0.097, aluminium is 0.508, phosphorus is 0.395.

In 6.0 quality % copper acetate (II) aqueous solution 107g, add above-mentioned zeolite 9.1g, stir more than 4 hours.Filter, after washing, dry in 100 ℃ of drying machines.Be 24 hours drying time.Use dry powder and 6.0 quality % copper acetate (II) aqueous solution 107g, repeatedly carry out same Copper Ion Exchange operation.Ion-exchange is all carried out 6 times repeatedly.Under the air draught of 120ml/ minute, at 750 ℃, the dry powder after 6 Copper Ion Exchange is fired 2 hours, obtain catalyst 8.Adopt the condition of catalytic evaluation 2, evaluate the NO purifying rate of this catalyst 8.Result is shown in table 3.

The TEM image of this catalyst 8 after measured, result is, as shown in Figure 7, owing to entering in zeolite crystal as ion, so can not observe copper particle on zeolite.Under the atmosphere that contains 10% steam, at 800 ℃, by catalyst 8 steam treatment after 5 hours, TEM image equally after measured, as shown in Figure 8, result is special variation not, on zeolite, can not observe copper particle.

Catalyst 8 is embedded in resin, with after the cutting of cross-sectional slice machine, measures EPMA, obtain element drawing, as shown in Figure 9, Cu all distributes equably, does not almost observe and detects local higher part.The coefficient of variation of trying to achieve the Cu strength ratio of each pixel of 200 × 200 is 15%.

In addition, the ammonia TPD of catalyst 8 after measured, result summit is 185 ℃.In addition, the ammonia adsorbance of catalyst 8 is 0.86mol/kg.

The NO-IR of catalyst 8 after measured, result is, at room temperature, 1860～1930cm ^-1region in only observe 1904cm ^-1peak.In addition, at 150 ℃, 1525～1757cm ^-1peak intensity with respect to 1757～1990cm ^-1peak intensity be 9.

The ESR spectrum of catalyst 8 after measured, result is to observe a kind of copper (II) ion of the value with g||=2.38.

[table 2]

[table 3]

The catalyst that comparative example 1A～4A obtains, its SCR catalyst activity below 175 ℃ is little.In addition, comparative example 1A～4A is in the time that be 60 minutes drying time, the residual 1 quality % that exceedes of the decentralized medium in mixture.Drying process is set as to 10 seconds catalyst of the present invention following or that obtain as the dry rapid draing of spraying, and its NOx purifying rate is high, shows higher activity in the low temperature below 175 ℃.Catalyst of the present invention is compared with the catalyst that adopts known method manufacture, and it demonstrates the activity of maximum 7.5 times at 150 ℃, and at least estimating also has 1.7 times, 7 times of maximums at 175 ℃, and minimum 1-3 is doubly.

< embodiment 1B～3B, comparative example 1B～3B>

The embodiment of 5th～9 modes of the present invention is as follows.

In embodiment and comparative example, carry out following physical property measurement, processing by following condition.

Water vapor adsorption isotherms:

At 120 ℃, sample is carried out after 5 hours vacuumizing, by water vapor adsorption amount determining device (ベ Le ソ mono-Block 18: Japanese ベ Le (strain) society system), the water vapor adsorption isotherms at measuring 25 ℃ by following condition.

Air thermostat temperature: 50 ℃

Adsorption temp: 25 ℃

Initial stage imports pressure: 3.0torr

Importing pressure setting is counted: 0

Saturation vapour pressure: 23.755torr

Equilibration time: 500 seconds

" steam treatment "

Zeolite of the present invention through steam treatment afterwards, supplies solid described later ²⁹si-DD/MAS-NMR spectroscopic measurement is used.Steam treatment in the present invention is undertaken by following step.The zeolite of 3g is filled in the quartz ampoule that internal diameter is 33mm, this quartz ampoule is arranged in cylinder type electric furnace.Under the state that the air of 100ml/min is circulated in packed layer, energising electric furnace, is warming up to 800 ℃ in 1 hour.Catalyst layer temperature reaches after 800 ℃, uses the pump of the liquor charging speed that is set as 0.6ml/h, and pure water is delivered to quartz ampoule.In the upstream of sufficiently high catalyst layer and more than 200 ℃ quartz ampoule parts inject pure water so that inject pure water vaporize completely in the upstream of catalyst layer.The pure water injecting is vaporized completely, and the steam of generation accounts for 10% of circulation airflow in catalyst layer.Through processing after 10 hours at 800 ℃ like this, stop the liquor charging of pump, place catalyst cool to room temperature.

" solid ²⁹si-DD/MAS-NMR wave spectrum "

Solid in the present invention ²⁹si-DD/MAS-NMR wave spectrum is, by through the zeolite sample of above-mentioned steam treatment in Shi Lanke test tube vacuum drying more than 2 hours after, in blanket of nitrogen down-sampling, using silicon rubber as standard substance, measure by following condition.

[table 4]

XRD determining condition

X-ray source: Cu-K α line

Power setting: 40kV-30mA

Optical condition when mensuration:

Divergent slit=1 °

Scatter slit=1 °

Be subject to optical slits=0.2mm

Position 2 θ (angle of diffraction) of diffraction maximum

Measurement range: 2 θ=3～60 degree

(embodiment 1B)

According to the disclosed method synthesized silicon-aluminum phosphate of embodiment 2 zeolite of Japanese Patent Laid-Open 2003-183020 communique.In water 253g, add lentamente 85% phosphatase 11 01g and boehmite (containing 25% water, サソ mono-Le society system) 68g, stir.Be made as A liquid.Different from A liquid, in addition aerosil (ァエロヅ Le 200: Japanese ァエロジ Le society system) 7.5g, morpholine 43.5g, triethylamine 55.7g, water 253g hybrid modulation are become to liquid.In this liquid, add at leisure A liquid, stir 3 hours, obtain aqueous gel.This aqueous gel is dropped into and is equipped with in the stainless steel autoclave of 1L of fluororesin inner core, and stir on limit, and limit is warming up to 190 ℃ with the programming rate of 16 ℃/h from 30 ℃ of straight lines, reacts 50 hours being up at 190 ℃ of Da Wendu.Being warming up in the process that is up to Da Wendu, the time stopping from the scopes of 80 ℃ to 120 ℃ is 2.5 hours.After reaction, through cooling, remove supernatant liquor by decant, reclaim sediment.After water washing and precipitating thing 3 times, filter, dry at 120 ℃.(by jet pulverizer, the zeolite obtaining is pulverized, making its median particle diameter is 3 μ m.) then at 560 ℃, under air draught, fire, remove template.

The zeolite obtaining is like this through XRD determining, and result is CHA structure

in addition, heating makes it to be dissolved in aqueous hydrochloric acid solution, carry out elementary analysis by icp analysis, result is with respect to the total of silicon, aluminium and the phosphorus of skeleton structure, and the composition (mol ratio) of each composition is that silicon is 0.088, aluminium is 0.500, phosphorus is 0.412.

The water vapor adsorption isotherms of this zeolite at 25 ℃ after measured, result is that the adsorbance variable quantity that is 0.04 to 0.09 from relative vapour pressure is 0.17g/g.

In addition, the water vapor adsorption isotherms at 25 ℃ after measured, result is that vapour pressure is that the water adsorption amount of 0.2 o'clock is 0.28g/g relatively.

For this zeolite, at 90 ℃, carry out the steam adsorption desorption test repeatedly (the adsorption desorption test repeatedly of the steam of 90-80-5) of 2000 times, result is that sustainment rate is 100%.In addition, measured the water vapor adsorption isotherms at 25 ℃ of sample after 2000 times, result is that vapour pressure is that the water adsorption amount of 0.2 o'clock is 0.27g/g relatively, is repeatedly 96% before adsorption desorption test.

Under the air draught of the 100ml/min that contains 10% steam, this zeolite 3g is carried out to steam treatment 10 hours at 800 ℃, by this solid after treatment ²⁹si-DD/MAS-NMR wave spectrum is shown in Figure 13.In Figure 13, with respect to the integrated intensity area of the signal strength signal intensity of-75～-125ppm, the integrated intensity area of the signal strength signal intensity of-99～-125ppm is 13%, and the integrated intensity area of the signal strength signal intensity of-105～-125ppm is 4%.

Use the aqueous solution of copper nitrate (II) to soak, make the zeolite as above obtaining be carried with the copper of 3 % by weight, be dried while break into pieces.Be 30 minutes drying time.Then, at 500 ℃, fire 4 hours, make SCR catalyst.

(embodiment 2B)

The aqueous solution that uses copper acetate, the zeolite that embodiment 1B is obtained is carried with the Cu metal of 3 % by weight, is dried.Dryly use spray dryer, be in 10 seconds drying time.After dry, at 750 ℃, fire 4 hours, make SCR catalyst.Measure with XRD, result is that observing at 21.4 degree is not the peak from CHA structure.

(embodiment 3B)

The aqueous solution that uses copper acetate, the zeolite that embodiment 1B is obtained is carried with the Cu metal of 3 % by weight, is dried.Dryly use spray dryer, be in 10 seconds drying time.After dry, at 500 ℃, fire 4 hours, make SCR catalyst.Measure with XRD, result is not observe peak at 21-4 degree.This SCR catalyst is placed after 5 hours under 800 ℃, the atmosphere of steam 10vol%, and with XRD determining, result is that observing at 21.4 degree is not the peak from CHA structure.

(embodiment 4B)

According to the disclosed method synthesized silicon-aluminum phosphate of embodiment 2 zeolite of Japanese Patent Laid-Open 2003-183020 communique.In water 150g, add lentamente 85% phosphoric acid 69.2g and boehmite (containing 25% water, サソ mono-Le society system) 48g, stir 2 hours.Add inward the water of pelletized silica 8.5g and 210g, make A liquid.Different from A liquid, then additional mixing morpholine 30.8g, triethylamine 35.7g, B liquid made.B liquid is joined to A liquid lentamente, stir 2 hours, obtain aqueous gel.Aqueous gel consist of 1Al ₂o ₃/ 0.4SiO ₂/ 0.85P ₂o ₅/ 1 morpholine/1 triethylamine/60H ₂o.This aqueous gel is dropped into and is equipped with in the stainless steel autoclave of 1L of fluororesin inner core, and stir on limit, and limit is warming up to 190 ℃ with the programming rate of 16 ℃/h from 30 ℃ of straight lines, reacts 24 hours being up at 190 ℃ of Da Wendu.Being warming up in the process that is up to Da Wendu, the time that the scope of 80 ℃ to 120 ℃ stops is 2.5 hours.After reaction, through cooling, remove supernatant liquor by decant, reclaim sediment.After water washing and precipitating thing 3 times, filter, dry at 100 ℃.With jet pulverizer, the dry powder obtaining being ground into median particle diameter is 3 μ m, then, at 550 ℃, under air draught, fires, and removes template.

in addition, through carrying out elementary analysis with icp analysis, the each composition of result is with respect to the composition (mol ratio) of the total of silicon, aluminium and the phosphorus of skeleton structure, and silicon is 0.12, and aluminium is 0.50, and phosphorus is 0.38.

This zeolite is carried out to 2000 steam adsorption desorption test repeatedly of 90-80-5, result is that sustainment rate is 86%.

The aqueous solution that uses copper acetate, makes the above zeolite obtaining be carried with the copper of 3 % by weight, after being dried, fires 2 hours at 750 ℃, makes SCR catalyst.

(embodiment 5B)

In water 74.3g, add 85% phosphoric acid 20.2g, then add boehmite (Pural SB, Condea system, the 75%Al of 13.6g ₂o ₃), stir 1 hour.In this mixture, add aerosil (ァエロジ Le 200) 1.5g, make A liquid.Different from A liquid, then modulate in addition the mixed solution of 35%TEAOH (tetraethyl ammonium hydroxide) aqueous solution 42.1g and isopropylamine 5.9g, make B liquid.In A liquid, add B liquid, stir 2 hours.This mixture is dropped into and is equipped with in the stainless steel autoclave of 1L of fluororesin inner core, and stir with the rotating speed of 150rpm on limit, and react 48 hours at 190 ℃ on limit.After reaction, adopt the method identical with embodiment 1B, obtain zeolite.With the result of this zeolite of XRD determining be CHA structure.In addition, with respect to the total of aluminium, phosphorus and the silicon of skeleton structure, the composition (mol ratio) of each composition through the result of elementary analysis be that silicon is 0.08, aluminium is 0.50, phosphorus is 0.42.

For this zeolite, at 90 ℃, carry out the steam adsorption desorption test repeatedly (the adsorption desorption test repeatedly of the steam of 90-80-5) of 2000 times, result is that sustainment rate is 92%.

Then, in copper acetate (II) monohydrate (キシダ chemistry society system) of 0.78g, add the pure water of 16g, make it to dissolve, add the above-mentioned zeolite of 8.0g, further stir, make water slurry.This water slurry is sprayed on 170 ℃ of metallic plates, makes it dry, make catalyst precursor.Under the condition in the circulation of air of 12ml/ minute for every 1g catalyst, at 750 ℃, catalyst precursor is fired 2 hours, obtain SCR catalyst.

(embodiment 6B)

Except the pulverizing zeolite described in the zeolite replacement embodiment 2B that use is not pulverized, other are the same with embodiment 2B, obtain SCR catalyst.The particle diameter of zeolite is 11O.Adopt the condition of catalyst reaction test 2, the NO purifying rate of the catalyst obtaining is evaluated.Result is shown in table 7.

(comparative example 1B)

Add aluminium isopropoxide 72g to stir at water 128g, then, add 85% phosphoric acid 39g, stir 1 hour.In this solution, add after aerosil (ァエロヅ Le 200) 1.2g, then add 35%TEAOH (tetraethyl ammonium hydroxide) aqueous solution 89g, stir 4 hours.This mixture is dropped into and is equipped with in the stainless steel autoclave of 500cc of fluororesin inner core, and stir with the rotating speed of 100rpm on limit, and react 48 hours at 180 ℃ on limit.After reaction, adopt the method identical with embodiment 1B, obtain zeolite.With the result of this zeolite of XRD determining be CHA structure.In addition, with respect to the total of aluminium, phosphorus and the silicon of skeleton structure, the composition (mol ratio) of each composition through the result of elementary analysis be that silicon is 0.033, aluminium is 0.491, phosphorus is 0.476.

(comparative example 2B)

In water 152g, add lentamente 85% phosphoric acid 69.2g and boehmite (containing 25% water, サソ-Le society system) 40.8g to stir.Set it as A liquid.Different from A liquid, then additional mixing aerosil (ァエロヅ Le 200) 7.2g, morpholine 52.2g, water 86.0g are modulated into solution.It is joined to A liquid lentamente, stir 3 hours, obtain having the aqueous gel of following composition.This aqueous gel is dropped into and is equipped with in the stainless steel autoclave of 1L of fluororesin inner core, and stir on limit, and limit is warming up to 190 ℃ with the programming rate of 16 ℃/h from 30 ℃ of straight lines, reacts 24 hours being up at 190 ℃ of Da Wendu.Being warming up in the process that is up to Da Wendu, the time that the scope of 80 ℃ to 120 ℃ stops is 2.5 hours.After reaction, adopt the method identical with embodiment 1B, obtain zeolite.The zeolite obtaining is like this CHA structure through the result of XRD determining.In addition, heating makes it to be dissolved in aqueous hydrochloric acid solution, carry out elementary analysis by icp analysis, result is with respect to the total of silicon, aluminium and the phosphorus of skeleton structure, and the composition (mol ratio) of each composition is that silicon is 0.118, aluminium is 0.496, phosphorus is 0.386.

(comparative example 3B)

In water 35.7g, add lentamente 85% phosphoric acid 28.8g and boehmite (containing 25% water, コ Application デァ society system) 17.0g, stir 2 hours.Add inward after aerosil (ァエロヅ Le 200) 3.0g, then add lentamente tetraethyl ammonium hydroxide (35% aqueous solution, ァ Le De リ Star チ system).This mixture is stirred 2 hours, make initial gel.This initial gel is dropped into and is equipped with in the stainless steel autoclave of 200cc of teflon (registered trade mark) inner core, and react 48 hours at 200 ℃ on rotation limit, limit.Cooling after reaction, remove supernatant liquor by centrifugation, reclaim sediment.By after the sediment washing obtaining, filter, dry at 100 ℃.It under air draught, fire 6 hours at 550 ℃, is obtained to zeolite.Powder X-ray RD after measured, result is that this zeolite is CHA type SAPO.In addition, carry out icp analysis, result is, with respect to the total of aluminium, phosphorus and the silicon of skeleton structure, the composition (mol ratio) of each composition is that silicon is 0.11, and aluminium is 0.49, and phosphorus is 0.40.

In addition, the water vapor adsorption isotherms at measuring 50 ℃, consequently vapour pressure is that the water adsorption amount of 0.2 o'clock is 0.26g/g relatively.At 90 ℃, carry out the steam adsorption desorption test repeatedly of 2000 times, consequently sustainment rate is 60%.In addition, measured sample after the 2000 times water vapor adsorption isotherms at 50 ℃, consequently vapour pressure is that the water adsorption amount of 0.2 o'clock is 0.14g/g relatively, is to carry out repeatedly 54% before adsorption desorption test.

Under the air draught of the 100ml/min that contains 10% steam, this zeolite 3g is heat-treated 10 hours at 800 ℃, by this solid after treatment ²⁹si-DD/MAS-NMR wave spectrum is shown in Figure 14.In Figure 14, with respect to the integrated intensity area of the signal strength signal intensity of-75～-125ppm, the integrated intensity area of the signal strength signal intensity of-99～-125ppm is 47%, and the integrated intensity area of the signal strength signal intensity of-105～-125ppm is 29%.

The aqueous solution that uses copper acetate, by ion-exchange, makes this zeolite be carried with Cu metal, after being dried, fires 4 hours at 500 ℃, makes SCR catalyst.Through XRD determining, except coming from the peak of CHA structure, do not observe other peak at 21.4 degree.

Under 800 ℃, the atmosphere of steam 10vol%, this SCR catalyst was placed after 5 hours, through XRD determining, do not observed peak at 21.4 degree.

(comparative example 4B)

Based on the disclosed information of US2009/0196812Al, with following method synthetic zeolite.In water 236.2g, add 85% phosphatase 79 8.2g, then add the boehmite (Pural SB, Condea system, 75%Al203) of 54.4g, stir 2 hours.In this mixture, add after morpholine 118.1g, at room temperature continue to stir, until the temperature of mixture becomes 28 ℃.Become after 28 ℃ in the temperature of mixture, add in the following order the pure water of the pure water of 1.8g, the silicon dioxide gel of 40.7g (LudoxAS40), 16.5g, stir 2 hours.This mixture is dropped into and is equipped with in the stainless steel autoclave of 1L of fluororesin inner core, stir with the rotating speed of 150rpm on limit, limit is warming up to 170 ℃ by autoclave in 8 hours consuming time, keeps the temperature 48 hours of 170 ℃, the material generation hydro-thermal reaction that the inside is filled.After reaction, adopt the method identical with embodiment 1, obtain zeolite.With the result of this zeolite of XRD determining be CHA structure.In addition, the result of elementary analysis is, with respect to the total of aluminium, phosphorus and the silicon of skeleton structure, the composition (mol ratio) of each composition is that silicon is 0.23.

For this zeolite, the result of carrying out the steam adsorption desorption test repeatedly (the adsorption desorption test repeatedly of the steam of 90-80-5) of 2000 times at 90 ℃ is that sustainment rate is 19%.

Then based on the disclosed information of US2009/0196812Al, with following method modulation catalyst.First, in the aqueous ammonium nitrate solution of 45g, add the pure water of 105g, make it to dissolve, add above-mentioned zeolite 15g.This mixed liquor is stirred on limit, and the ammonia spirit that limit drips lmoL/L after making pH be 3.2, carries out ammonium ion exchange, filtration, the washing of l hour at 80 ℃.Repeatedly carry out this operation, the dry filter cake obtaining at 100 ℃, obtains ammonium type zeolite.In copper acetate (II) monohydrate (キッダ chemistry society system) of 2.4g, add the pure water of 60g, make it to dissolve, add the above-mentioned ammonium type zeolite of 15.0g, make it to carry out the Copper Ion Exchange of 1 hour at 70 ℃, after filtration, water punching, dry at 100 ℃.The dry powder obtaining is fired 1 hour at 400 ℃, obtained comparison catalyst.Adopt the condition of catalyst reaction test 2, the NO purifying rate that compares catalyst is evaluated.Result is shown in table 7.

< catalyst reaction test 1>

Carry out the steam adsorption desorption test repeatedly (the adsorption desorption test repeatedly of the steam of 90-80-5) of catalyst, obtain sustainment rate.The results are shown in table 6.

By after the catalyst punch forming of modulation, to break into pieces, whole grain becomes 16～28 orders.Each catalyst 5cc that whole grain is crossed is filled in atmospheric fixed bed flow type reaction tube.At 150 ℃, make ammonia in catalyst layer, circulate 10 minutes, make catalyst adsorb ammonia.Limit circulates the gas of the composition of table 5 with space velocity SV=30000/h in catalyst layer, and the rate of removing of the nitrogen oxide of stability is evaluated on limit at the temperature of 150～200 ℃.The rate of removing at 175 ℃ is shown in Table 6.

< catalyst reaction test 2>

Catalytic amount is changed to 1cc, SV is changed to 100,000/h, in addition, other employings are tested 1 identical method with catalyst reaction, measure the purifying rate of nitrogen oxide.

< hydro-thermal long duration test >

By the SCR catalyst of removing rate described in having evaluated under 800 ℃, the atmosphere of the steam of 10 volume %, space velocity SV=3000/h, circulate 5 hours, carry out after hydrothermal treatment consists, carry out same catalyst reaction test, the persistence with respect to high-temperature vapor is evaluated.The results are shown in table 7.

The steam of the 90-60-5 of < catalyst is adsorption desorption long duration test > repeatedly

As the repeatedly adsorption desorption experimental condition approaching with actual installation condition, implement " the adsorption desorption test repeatedly of the steam of 90-60-5 " of catalyst.As the test of adsorption desorption repeatedly of steam, except 80 ℃ of saturated steam atmosphere are changed to 60 ℃ of saturated steam atmosphere, carry out identical described " the adsorption desorption test repeatedly of the steam of 90-80-5 " test, based on the condition of above-mentioned catalyst reaction test 2, the NO purifying rate of the sample of testing rear recovery is evaluated.2.0g catalyst is packed in 4 sample containers separately according to every part of 0.5g, implement respectively the steam adsorption desorption test repeatedly of 90-60-5.The number of occurrence of adsorption desorption is 2000 times.From 4 containers, reclaim through the steam sample of adsorption desorption repeatedly, based on the condition of catalyst reaction test 2, evaluate its NO purifying rate, evaluate with respect to the durability of the catalyst of adsorption desorption repeatedly.The results are shown in table 8.

The condition repeatedly approaching with actual installation condition has been reproduced in this test.In the waste gas of the Diesel engines such as automobile, generally contain the water of 5～15 volume %.In the time of running car, waste gas is in more than 200 ℃ high temperature, and relative humidity is reduced to below 5%, the state of catalyst in desorption moisture.But in the time that automobile stops, temperature is near 90 ℃, and relative humidity becomes more than 15%, catalyst adsorbed water.According to this condition, in the time carrying out adsorbing at 90 ℃, relative humidity is 28%.Seem very important close to the repeated durability under physical condition state during in actual installation at this.

SCR catalyst described in embodiment 1B, in the catalyst reaction test after hydrothermal durability test, its nitrogen oxide rate of removing is 99%, does not see caused by hydrothermal durability test deteriorated.

Because 800 ℃, the atmosphere of 10 volume % are close to the atmosphere at the temperature of the diesel engine automobile waste gas of supposition, so, low this fact of degradation under this condition is most important in practical application.

[table 5]

The gas composition of catalyst reaction test

[table 6]

[table 7]

[table 8]

Although the present invention at length and with reference to specific embodiment is illustrated, and the various changes or the correction that apply without departing from the spirit and scope of the present invention, will be readily apparent to persons skilled in the art.The Japanese patent application (special Willing 2009-169338) that the application applied for take the Japanese patent application (special Willing 2009-011590) of application on January 22nd, 2009, the Japanese patent application (special Willing 2009-118945) of application on May 15th, 2009, the Japanese patent application (special Willing 2009-141397) of application on June 12nd, 2009, on July 17th, 2009, the Japanese patent application (special Willing 2009-291476) of application on December 22nd, 2009, as basis, are introduced its content in this as reference.

Utilizability in industry

The manufacture method of catalyst for cleaning up nitrogen oxides of the present invention can provide active high catalyst for cleaning up nitrogen oxides by easy method.

In addition, the catalyst for cleaning up nitrogen oxides of the application of the invention, can provide the catalyst that purification of nitrogen oxides power is high, and the suitable cheap exhaust gas catalyst of removing the nitrogen oxide in waste gas in waste gas, Diesel engine is especially provided.Further also can be for the purification of the nitrogen oxide in atmosphere.

Claims

1. a catalyst for cleaning up nitrogen oxides, it is characterized in that, be the catalyst for cleaning up nitrogen oxides that contains zeolite, and this catalyst at least contains silicon atom, phosphorus atoms, aluminium atom, the steam of measuring at 90 ℃ is repeatedly in adsorption desorption test, and Adsorption Dimension holdup is more than 80%.

2. catalyst for cleaning up nitrogen oxides according to claim 1, in the described steam front and back of adsorption desorption test repeatedly, the relative vapour pressure that this catalyst is measured in 25 ℃ of water vapor adsorption isotherms is the water adsorption amount of 0.2 o'clock while measuring, and the ratio of the water adsorption amount of the water adsorption amount after described test before with respect to described test is more than 0.7.

3. catalyst for cleaning up nitrogen oxides according to claim 1, is characterized in that, zeolite at least contains silicon atom, phosphorus atoms, aluminium atom, and the steam of measuring at 90 ℃ is repeatedly in adsorption desorption test, and Adsorption Dimension holdup is more than 80%.

4. a catalyst for cleaning up nitrogen oxides, it is characterized in that, be the catalyst for cleaning up nitrogen oxides that contains zeolite, and this zeolite at least contains silicon atom, phosphorus atoms, aluminium atom, the steam of measuring at 90 ℃ is repeatedly in adsorption desorption test, and Adsorption Dimension holdup is more than 80%.

5. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, in the described steam front and back of adsorption desorption test repeatedly, the relative vapour pressure that described zeolite is measured in 25 ℃ of water vapor adsorption isotherms is the water adsorption amount of 0.2 o'clock while measuring, and the ratio of the water adsorption amount of the water adsorption amount after described test before with respect to described test is more than 0.7.

6. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, under the atmosphere that contains 10% steam, at 800 ℃, described zeolite was carried out to steam treatment after 10 hours, measure solid ²⁹when Si-DD/MAS-NMR wave spectrum, the integrated intensity area of the signal strength signal intensity of one 105～mono-125ppm is below 25% with respect to the integrated intensity area of the signal strength signal intensity of one 75～mono-125ppm.

7. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, described catalyst is in the X-ray diffraction mensuration that uses CuK α as x-ray source, except the peak from zeolite, also in being the scope more than 21.2 degree, below 21.6 degree, the angle of diffraction 20 observes diffraction maximum.

8. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, after described catalyst being heat-treated more than 700 ℃, while carrying out described X-ray diffraction mensuration, except the peak from zeolite, also in being the scope more than 21.2 degree, below 21.6 degree, the angle of diffraction 2 θ observe diffraction maximum.

9. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, it is characterized in that, this zeolite is carried with metal.

10. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, in skeleton structure by silicon atom with respect to zeolite the total of contained aluminium atom, silicon atom, phosphorus atoms exist ratio to be made as x time, x is more than 0.05, below 0.11, the ratio that exists of aluminium atom is made as y, phosphorus atoms exist ratio to be made as z time, y is more than 0.3, below 0.6, and z is more than 0.3, below 0.6.

11. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, in skeleton structure by silicon atom with respect to described zeolite the total of contained aluminium atom, silicon atom and phosphorus atoms exist ratio to be made as x time, x is between 0.08 to 0.11, the ratio that exists of aluminium atom is made as y, phosphorus atoms exist ratio to be made as z time, y is more than 0.3, below 0.6, and z is more than 0.3, below 0.6.

12. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, in skeleton structure by silicon atom with respect to described zeolite the total of contained aluminium atom, silicon atom and phosphorus atoms exist ratio to be made as x time, x is between 0.088 to 0.11, the ratio that exists of aluminium atom is made as y, phosphorus atoms exist ratio to be made as z time, y is more than 0.3, below 0.6, and z is more than 0.3, below 0.6.

13. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, it is characterized in that, it for being carried with the catalyst for cleaning up nitrogen oxides that metal forms on zeolite, in the skeleton structure of described zeolite, at least contain aluminium atom, silicon atom and phosphorus atoms, and the average grain diameter of described zeolite is more than 1 μ m.

14. according to the catalyst for cleaning up nitrogen oxides described in claim 1 or 4, and the structure of described zeolite is CHA in the code of IZA regulation.

15. catalyst for cleaning up nitrogen oxides according to claim 9, described metal is Cu or Fe.